Abstract
The present study was carried out in the frame of the optimization of the synthesis process of 1,1,4,4-tetramethyl-2-tetrazene (TMTZ), a prospective liquid propellant. The liquid–liquid (LL) equilibria of the TMTZ + H2O binary system were studied under atmospheric pressure and in the temperature range from 278.15 up to 348.15 K. These results established the conditions leading to a spontaneous demixing of TMTZ from the aqueous synthesis solutions. The experimental study of the liquid–vapor (LV) equilibria of the TMTZ + H2O system using DSC, under atmospheric pressure, highlighted the various equilibrium domains involved in the distillation step. Besides, a heteroazeotropic invariant was identified at TH = 366.3 K for x (TMTZ) = 0.254. Lastly, the thermodynamic modeling of those equilibria, using various models (Van Laar, NRTL, Wilson), enabled to improve the experimental results in order to enhance the extraction conditions leading to the production of ultra-pure TMTZ.
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References
Catoire L, Chaumeix N, Pichon S, Paillard C. Visualizations of gas-phase NTO/MMH reactivity. J Propul Power. 2006;22(1):120–6.
Frank I, Hammerl A, Klapoetke TM, Nonnenberg C, Zewen H. Processes during the hypergolic ignition between monomethylhydrazine (MMH) and dinitrogen tetroxide (N2O4) in rocket engines. Prop Explos Pyrotech. 2005;30:44–52.
Nonnenberg C, Frank I, Klapoetke TM. Ultrafast cold reactions in the bipropellant monomethylhydrazine/nitrogen tetroxide: CPMD simulations. Angew Chem. 2004;43(35):4585–9.
Osmont A, Catoire L, Klapotke TM, Vaghjiani GL, Swihart MT. Thermochemistry of species potentially formed during NTO/MMH hypergolic ignition. Prop Explos Pyrotech. 2008;33:209–12.
Sutton GP. History of liquid propellant rocket engines in the united states. J Propul Power. 2003;19(6):978–1007.
Schmidt EW. Hydrazine and its derivatives: preparation, properties, applications. New York: John Wiley and Sons; 1984.
Carlsen L, Kenesova OA, Batyrbekova SE. A preliminary assessment of the potential environmental and human health impact of unsymmetrical dimethylhydrazine as a result of space activities. Chemosphere. 2007;67:1108–16.
Carlsen L, Kenessov BN, Batyrbekova SY, Kolumbaeva SZ, Shalakhmetova TM. Assessment of the mutagenic effect of 1,1-dimethyl hydrazine. Environ Toxicol Pharmacol. 2009;28:448–52.
Choudhary G, Hansen H. Human health perspective on environmental exposure to hydrazines: a review. Chemosphere. 1998;37(5):801–43.
Reddy G, Song J, Mecchi MS, Johnson MS. Genotoxicity assessment of two hypergolic energetic propellant compounds. Mutat Res Genet Toxicol Environ Mutagen. 2010;700(1–2):26–31.
Dhenain A, Darwich C, Sabate CM, Le DM, Bougrine AJ, Delalu H, Lacôte E, Payen L, Guitton J, Labarthe E, Jacob G. (E)-1,1,4,4-Tetramethyl-2-tetrazene (TMTZ): a prospective alternative to hydrazines in rocket propulsion. Chem Eur J. 2017;23(41):9897–907.
Sabate CM, Delalu H, Guelou Y, Dhenain A, Perut C. Process for preparing alkyltetrazenes. FR2974087A1; 2012.
Mokdad S, Georgin E, Mokbel I, Jose J, Hermier Y, Himbert M. On the way to determination of the vapor-pressure curve of pure water. Int J Thermophys. 2012;33(8–9):1374–89.
Kemme HR, Kreps SI. Vapor pressure determination by differential thermal analysis. Anal Chem. 1969;41(13):1869–72.
Vassallo DA, Harden JC. Precise phase transition measurements of organic materials by differential thermal analysis. Anal Chem. 1962;34(1):132–5.
Akisawa Silva LY, Matricarde Falleiro RM, Meirelles AJA, Kraehenbuehl MA. Vapor-liquid equilibrium of fatty acid ethyl esters determined using DSC. Thermochim Acta. 2011;512(1–2):178–82.
Liu ZR, Shao YH. Measurement of the eutectic composition and temperature of energetic materials. Part 1. The phase-diagram of binary systems. Thermochim Acta. 1995;250(1):65–76.
Wong DSH, Sandler SI. A theoretically correct mixing rule for cubic equations of state. AICHE J. 1992;38(5):671–80.
Stull DR. Vapor pressure of pure substances—organic compounds. Ind Eng Chem. 1947;39(4):517–40.
Gmehling J. Data bases of the Dortmund Data Bank, UNIFAC Consortium, http://www.ddbst.com/published-parameters-unifac.html#ListOfSubGroupsAndTheirGroupSurfacesAnVolumes.
Van Laar JJ. Die Schmelz- oder Erstarrungskurven bei binären Systemen, wenn die feste Phase ein Gemisch (amorphe feste Lösung oder Mischkristalle) der beiden Komponenten ist. Z Phys Chem. 1908;63:216–53.
Wilson GM. Vapor-liquid equilibrium: a new expression for the excess free energy of mixing. J Am Chem Soc. 1964;86(2):127–30.
Renon H, Prausnitz JM. Local composition in thermodynamic excess functions for liquid mixtures. AIChE J. 1968;14(1):135–44.
Renon H, Prausnitz J. Estimation of parameters for NRTL equation for excess Gibbs energies of strongly nonideal liquid mixtures. Ind Eng Chem Process Des Dev. 1969;8(3):413–9.
Bondi A. Van der Waals volumes and radii. J Phys Chem. 1964;68(3):441–51.
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This work was supported by Université Claude Bernard Lyon 1, CNRS, CNES and ArianeGroup, which are gratefully acknowledged.
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Bougrine, AJ., Renault, A., Frangieh, MR. et al. Measurements of isobaric LLV equilibria of the 1,1,4,4-tetramethyl-2-tetrazene-water binary system: novel experimental approach and modeling essays. J Therm Anal Calorim 147, 6869–6881 (2022). https://doi.org/10.1007/s10973-021-10987-w
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DOI: https://doi.org/10.1007/s10973-021-10987-w