Advanced Space Storable Propellants for Outer Planet Exploration

Thunnissen, Daniel P.; Guernsey, Carl S.; Baker, Raymond S.; Miyake, Robert N.

doi:10.2514/6.2004-3488

Cited by 7 publications

(4 citation statements)

References 4 publications

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“…The most commonly used space-storable bipropellant is the mixture of fluorine and hydrazine, 2 which can provide desirable propulsion for a wide variety of unmanned planetary explorations owing to its large specific impulse (I sp ) and high condensed density. 3 To accurately model the combustion of F 2 /N 2 H 4 bipropellants, extensive experimental and theoretical research has been performed to investigate the decomposition mechanisms and the kinetics of the involved reactions in the past several decades. [4][5][6][7][8][9][10] But N 2 H 4 has its own limitations, such as less thermodynamic stability and less remaining-liquid-state ability over a wide temperature range.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Study of the F + CH₃NHNH₂ Reaction Mechanism

Ding

Luo

2010

J. Phys. Chem. A

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The F + CH(3)NHNH(2) reaction mechanism is studied based on ab initio quantum chemistry methods as follows: the minimum energy paths (MEPs) are computed at the UMP2/6-311++G(d,p) level; the geometries, harmonic vibrational frequencies, and energies of all stationary points are predicted at the same level of theory; further, the energies of stationary points and the points along the MEPs are refined by UCCSD(T)/6-311++g(3df,2p). The ab initio study shows that, when the F atom approaches CH(3)NHNH(2), the heavy atoms, namely N and C atoms, are the favorable combining points. For the two N atoms, two prereaction complexes with C(s) symmetry are generated and there exists seven possible subsequent reaction routes, of which routes 1, 2, 5, and 7 are the main channels. Routes 1, 2, and 5 are associated with HF elimination, with H from the amino group or imido group, and route 7 involves the N-N bond break. Routes 3 and 6 with relation to HF elimination with H from methyl, and route 4 involved the C-N bond break, are all energetically disfavored. For the C atom, the attack of F results in the break of the C-N bond and the products are CH(3)F + NHNH(2). This route is very competitive.

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Section: Introductionmentioning

confidence: 99%

Ab Initio Study of the F + CH₃NHNH₂ Reaction Mechanism

Ding

Luo

2010

J. Phys. Chem. A

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“…As compared to the conventional earth-storable bipropellant (N 2 O 4 /CH 3 NHNH 2 ), the combination of fluorine and hydrazine (F 2 /N 2 H 4 ) has been selected as the most attractive space-storable bipropellant 2 to provide the necessary spacecraft propulsion for a wide variety of scientifically interesting unmanned planetary explorations due to its extremely large specific impulse (I sp ) and the very high condensed density. 3 F 2 and N 2 H 4 are both highly reactive species. N 2 H 4 is one of the rare endothermic compounds, whose decomposition can lead to self-ignition, 4 detonation, 4,5 or a stable flame without any oxidizer.…”

Section: Introductionmentioning

confidence: 98%

“…These propellants are usually utilized with different oxidizers in rocket motors to generate the desired thrust. As compared to the conventional earth-storable bipropellant (N 2 O 4 /CH 3 NHNH 2 ), the combination of fluorine and hydrazine (F 2 /N 2 H 4 ) has been selected as the most attractive space-storable bipropellant to provide the necessary spacecraft propulsion for a wide variety of scientifically interesting unmanned planetary explorations due to its extremely large specific impulse ( I sp ) and the very high condensed density …”

Section: Introductionmentioning

confidence: 99%

Direct Dynamics Study on the Reaction of N₂H₄ with F Atom: A Hydrogen Abstraction Reaction?

Zhang

2006

J. Phys. Chem. A

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We present a systematic direct ab initio dynamics investigation of the reaction between N2H4 and F atom, which is predicted to have three possible reaction channels. The structures and frequencies at the stationary points and the points along the minimum energy paths (MEPs) of all reaction channels were calculated at the UB3LYP/6-31+G(d,p) level of theory. Energetic information of stationary points and the points along the MEPs was further refined by means of the CCSD(T)/aug-cc-pVTZ method. The calculated results revealed that the first two primary channels (N2H4+F-->N2H3+HF) are equivalent and occur synchronously via the formation of a pre-reaction complex with Cs symmetry rather than via the direct H abstraction. The pre-reaction complex then evolves into a hydrogen-bonding intermediate through a transition state with nearly no barrier and a high exothermicity, which finally makes the intermediate further decompose into N2H3 and HF. Another reaction channel of minor role (N2H4+F-->NH2F+NH2) was also found during the calculations, which has the same Cs pre-reaction complex but forms NH2F and NH2 via another transition state with high-energy barrier and low exothermicity. The rate constants of these channels were calculated using the improved canonical variational transition state theory with the small-curvature tunneling correction (ICVT/SCT) method. The three-parameter ICVT/SCT rate constant expressions of k(ICVT/SCT) at the CCSD(T)/aug-cc-pVTZ//UB3LYP/6-31+G(d,p) level of theory within 220-3000 K were fitted as (7.64x10(-9))T (-0.87) exp(1180/T) cm3 mole-1 s-1 for N2H4+F-->N2H3+HF and 1.45x10(-12)(T/298)(2.17) exp(-1710/T) cm3 mole-1 s-1 for N2H4+F-->NH2F+NH2.

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“…However, high-pressure chemistry of hydrocarbons as a science started to develop only recently, -primarily due to the unavailability of the specific equipment for the experiments. To date, only methane, the first member of the alkane homologous series, has been investigated when subjected to a wide range of pressures and temperatures 1-4 , because of its widespread occurrence in geological systems 5-7 and well-known role in the atmosphere of the Solar System's outer planets 8,9 . The behavior of other hydrocarbons, both unsaturated 10,11 and saturated 12,13 , have been less widely investigated with the use of various high-pressure techniques.The focus on the significance of methane's high-pressure high-temperature behavior implies that the fate of higher hydrocarbons has been ignored.…”

mentioning

confidence: 99%

Raman Spectroscopy Study on Chemical Transformations of Propane at High Temperatures and High Pressures

Kudryavtsev

Fedotenko

Koemets

et al. 2020

Sci Rep

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this study is devoted to the detailed in situ Raman spectroscopy investigation of propane c 3 H 8 in laserheated diamond anvil cells in the range of pressures from 3 to 22 GPa and temperatures from 900 to 3000 K. We show that propane, while being exposed to particular thermobaric conditions, could react, leading to the formation of hydrocarbons, both saturated and unsaturated as well as soot. Our results suggest that propane could be a precursor of heavy hydrocarbons and will produce more than just sooty material when subjected to extreme conditions. These results could clarify the issue of the presence of heavy hydrocarbons in the earth's upper mantle.Thermal and catalytic transformations of various hydrocarbon compounds at normal pressure have attracted significant attention in the field of petrochemistry. However, high-pressure chemistry of hydrocarbons as a science started to develop only recently, -primarily due to the unavailability of the specific equipment for the experiments. To date, only methane, the first member of the alkane homologous series, has been investigated when subjected to a wide range of pressures and temperatures 1-4 , because of its widespread occurrence in geological systems 5-7 and well-known role in the atmosphere of the Solar System's outer planets 8,9 . The behavior of other hydrocarbons, both unsaturated 10,11 and saturated 12,13 , have been less widely investigated with the use of various high-pressure techniques.The focus on the significance of methane's high-pressure high-temperature behavior implies that the fate of higher hydrocarbons has been ignored. Though the high-pressure, high-temperature (HPHT) behavior of ethane has been investigated several times 12,14 , propane has only been studied at ambient temperatures 15,16 . Propane is the third most abundant hydrocarbon on Earth after methane and ethane. It has been detected in the atmosphere of outer planets 17 and their satellites 18 , and is a typical product of HPHT hydrocarbon synthesis performed both for chemical and geological purposes 19,20 .The relevance of the investigation of carbon-bearing compounds can be understood from the perspective of the growing evidence of the role of hydrocarbon compounds deep in the Earth's interior, which could contribute to the global carbon cycle 21,22 . Unfortunately, even for methane, investigations into its behavior under conditions of high pressure have yielded inconclusive and mutually conflicting results.Propane's importance as a petrochemical feedstock led to detailed studies of its thermal transformations in the range of 500-900 °C in processes such as pyrolysis and thermal cracking [23][24][25] . By changing the basic conditions of the process, the content of hydrocarbon compounds complex systems could be varied from higher normal and isoalkanes, dienes, arenes, and alkenes to C 1 -C 3 fractions. These thermal processes were only investigated in the diapason under relatively mild pressures because of the process goal-low pressures are favorable for the synthesis of low-molecul...

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Advanced Space Storable Propellants for Outer Planet Exploration

Cited by 7 publications

References 4 publications

Ab Initio Study of the F + CH₃NHNH₂ Reaction Mechanism

Ab Initio Study of the F + CH₃NHNH₂ Reaction Mechanism

Direct Dynamics Study on the Reaction of N₂H₄ with F Atom: A Hydrogen Abstraction Reaction?

Raman Spectroscopy Study on Chemical Transformations of Propane at High Temperatures and High Pressures

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Advanced Space Storable Propellants for Outer Planet Exploration

Cited by 7 publications

References 4 publications

Ab Initio Study of the F + CH3NHNH2 Reaction Mechanism

Ab Initio Study of the F + CH3NHNH2 Reaction Mechanism

Direct Dynamics Study on the Reaction of N2H4 with F Atom: A Hydrogen Abstraction Reaction?

Raman Spectroscopy Study on Chemical Transformations of Propane at High Temperatures and High Pressures

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Product

Resources

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Ab Initio Study of the F + CH₃NHNH₂ Reaction Mechanism

Ab Initio Study of the F + CH₃NHNH₂ Reaction Mechanism

Direct Dynamics Study on the Reaction of N₂H₄ with F Atom: A Hydrogen Abstraction Reaction?