Thermal Decomposition of Hydrazines from Reactive Dynamics Using the ReaxFF Reactive Force Field

We report reactive dynamics (RD) studies on: the decomposition of bulk hydrazine (N_2H_4); the decomposition of bulk monomethyl-hydrazine (CH_3N_2H_3), hereafter referred to simply as methyl-hydrazine; the decomposition of hydrazine in the presence of hydrogen peroxide (H_2O_2); and decomposition hydrazine on catalytic surfaces Pt[100] and Pt[111] under various conditions. These studies use the ReaxFF reactive force field to describe the multitude of chemical reactions in these systems for a variety of reaction conditions in order to show that this approach leads to realistic decomposition mechanisms and rates. In particular, we determined how the decomposition of hydrazine is affected by temperature, pressure, and heating rate. We analyzed chemical reaction mechanism of the decomposition of hydrazine at the studied conditions and found that at lower temperatures the initial product from hydrazine decomposition is NH_3, whereas at higher temperatures H_2 and N_2 are the dominant early products. Prominent intermediates observed during these decompositions include N_2H_3, N_2H_2, and NH_2, in agreement with quantum mechanical studies (7.3 ps at 3000 K). As the heating rate is decreased, the onset for hydrazine decomposition shifts to lower temperatures. Using a constant heating rate, we found that higher pressure (increased density) favors formation of NH_3 over N_2 and H_2. In studies of the catalytic decomposition of hydrazine on surfaces Pt[100] and Pt[111], we found that the presence of a Pt-catalyst reduces the initial decomposition temperature of hydrazine by about 50%. We found that the Pt[100]-surface is 20 times more active for hydrazine decomposition than the Pt[111]-surface, in qualitative agreement with experiments. These studies indicate how ReaxFF RD can be useful in understanding the chemical processes involved in bulk and catalytic decomposition and in oxidation of reactive species under various reaction conditions

Hydrazine monitoring in spacecraft

Hydrazine (HZ) and monomethyl hydrazine (MMH) are highly toxic compounds used as fuels in the Space Shuttle Orbiter Main Engines and in its maneuvering and reaction control system. Satellite refueling during a mission may also result in release of hydrazines. During extravehicular activities, the potential exists for hydrazines to contaminate the suit and to be brought into the internal atmosphere inadvertantly. Because of the high toxicity of hydrazines, a very sensitive, reliable, interference-free, and real-time method of measurement is required. A portable ion mobility spectrometer (IMS) has exhibited a low ppb detection limit for hydrazines suggesting a promising technology for the detection of hydrazines in spacecraft air. The Hydrazine Monitor is a modified airborne vapor monitor (AVM) with a custom-built datalogger. This off-the-shelf IMS was developed for the detection of chemical warfare agents on the battlefield. After early evaluations of the AVM for hydrazine measurements showed a serious interference from ammonia, the AVM was modified to measure HZ and MMH in the ppb concentration range without interference from ammonia in the low ppm range. A description of the Hydrazine Monitor and how it functions is presented

Preparation of substituted hydrazines

Thesis (M.A.)--Boston UniversityAlthough a large number of substituted hydrazines are known, the preparation of simple monoalkylhydrazines in a manner suitable for the large-scale economical synthesis has never been developed. Three methods commonly employed in the laboratory i.e. the direct alkylation of hydrazine by an alkyl halide, the alkylation of benzalazine with alkyl sulfates and the catalytic reduction of hydrazones all have serious limitations. It appears that the reduction of an N-nitro or N-nitroso group should give a hydrazine derivative if the reduction could be carried out under conditions which would reduce these groups without scission of the nitrogen to nitrogen bond. Such reductions of a few compounds, notably N-methyl-N-nitrosourea, have been known for some time but the yields are either low or not given in the literature in most cases. The current research project was directed toward the development of suitable conditions for this desired reduction without hydrogenolysis of the N-N bond. Many possible reducing agents are known and should be investigated; the present paper deals only with the reduction of these compounds with zinc dust and dilute acetic acid [TRUNCATED

Groups 5 and 6 Terminal Hydrazido(2−) Complexes: N_β Substituent Effects on Ligand-to-Metal Charge-Transfer Energies and Oxidation States

Brightly colored terminal hydrazido(2−) (dme)MCl_3(NNR_2) (dme = 1,2-dimethoxyethane; M = Nb, Ta; R = alkyl, aryl) or (MeCN)WCl_4(NNR_2) complexes have been synthesized and characterized. Perturbing the electronic environment of the β (NR_2) nitrogen affects the energy of the lowest-energy charge-transfer (CT) transition in these complexes. For group 5 complexes, increasing the energy of the N_β lone pair decreases the ligand-to-metal CT (LMCT) energy, except for electron-rich niobium dialkylhydrazides, which pyramidalize N_β in order to reduce the overlap between the Nb═Nα π bond and the Nβ lone pair. For W complexes, increasing the energy of N_β eventually leads to reduction from formally [W^(VI)≡N–NR_2] with a hydrazido(2−) ligand to [W^(IV)═N═NR_2] with a neutral 1,1-diazene ligand. The photophysical properties of these complexes highlight the potential redox noninnocence of hydrazido ligands, which could lead to ligand- and/or metal-based redox chemistry in early transition metal derivatives

Readily accessible sp3-rich cyclic hydrazine frameworks exploiting nitrogen fluxionality

Increased molecular complexity correlates with improved chances of success in the drug development process. Here, a strategy for the creation of sp3-rich, non-planar heterocyclic scaffolds suitable for drug discovery is described that obviates the need to generate multiple stereogenic centers with independent control. Asymmetric transfer hydrogenation using a tethered Ru-catalyst is used to efficiently produce a range of enantiopure cyclic hydrazine building blocks (up to 99% ee). Iterative C–N functionalization at the two nitrogen atoms of these compounds produces novel hydrazine and hydrazide based chemical libraries. Wide chemical diversification is possible through variation in the hydrazine structure, use of different functionalization chemistries and coupling partners, and controlled engagement of each nitrogen of the hydrazine in turn. Principal Moment of Inertia (PMI) analysis of this small hydrazine library reveals excellent shape diversity and three-dimensionality. NMR and crystallographic studies confirm these frameworks prefer to orient their substituents in three-dimensional space under the control of a single stereogenic center through exploitation of the fluxional behavior of the two nitrogen atoms

An annotated bibliography of propellant processing methods

The author has specialized in space resources research for many years, with special emphasis on oxygen reduction methods. He has been retained to write a comprehensive review of these methods, detailing advantages and disadvantages, listing by-products and presenting recommendations. As the first step, an extensive outline was prepared, and the portion of this outline covering product manufacture was selected as the initial goal. A working version is presented

Gas chromatographic column enables analysis of propellant hydrazines

Stainless steel column is used in gas chromatographic analysis of propellant-grade hydrazine. The column has also been found effective for the separation of other amines and alcohols and nitriles

A study for hypergolic vapor sensor development

In summary, the following tasks were completed within the scope of this work: (1) a portable Monomethylhydrazine analyzer was developed, designed, fabricated and tested. (2) A portable NO2 analyzer was developed, designed, fabricated and tested. (3) Sampling probes and accessories were designed and fabricated for this instrumentation. (4) Improvements and modifications were made to the model 7630 Ecolyzer in preparation for field testing. (5) Instrument calibration procedures and hydrazine handling techniques necessary to the successful application of this hardware were developed