• Medientyp: E-Artikel
  • Titel: Calculation of Some Thermodynamic Properties and Detonation Parameters of 1‐Ethyl‐3‐Methyl‐H‐Imidazolium Perchlorate, [Emim][ClO4], on the Basis of CBS‐4M and CHEETAH Computations Supplemented by VBT Estimates
  • Beteiligte: Klapötke, Thomas M.; Stierstorfer, Jörg; Brooke Jenkins, H. Donald; van Eldik, Rudi; Schmeisser, Matthias
  • Erschienen: Wiley, 2011
  • Erschienen in: Zeitschrift für anorganische und allgemeine Chemie
  • Umfang: 1308-1313
  • Sprache: Englisch
  • DOI: 10.1002/zaac.201100144
  • ISSN: 0044-2313; 1521-3749
  • Schlagwörter: Inorganic Chemistry
  • Zusammenfassung: <jats:title>Abstract</jats:title><jats:p>This paper estimates some thermochemical (in kcal mol<jats:sup>–1</jats:sup>) and detonation parameters for the ionic liquid, [emim][ClO<jats:sub>4</jats:sub>] and its associated solid in view of its investigation as an energetic material. The thermochemical values estimated, employing CBS‐4M computational methodology and volume‐based thermodynamics (VBT) include: lattice energy, <jats:italic>U</jats:italic><jats:sub>POT</jats:sub>([emim][ClO<jats:sub>4</jats:sub>]) ≈︁ 123 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup>; enthalpy of formation of the gaseous cation, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic>°([emim]<jats:sup>+</jats:sup>, g) = 144.2 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and anion, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic>°([ClO<jats:sub>4</jats:sub>]<jats:sup>–</jats:sup>, g) = –66.1 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup>; the enthalpy of formation of the solid salt, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic>°([emim][ClO<jats:sub>4</jats:sub>],s) ≈︁ –55 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and for the associated ionic liquid, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic><jats:sup>o</jats:sup>([emim][ClO<jats:sub>4</jats:sub>],l) = –52 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> as well as the corresponding Gibbs energy terms: Δ<jats:sub>f</jats:sub><jats:italic>G</jats:italic>°([emim][ClO<jats:sub>4</jats:sub>],s) ≈︁ +29 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and Δ<jats:sub>f</jats:sub><jats:italic>G</jats:italic><jats:sup>o</jats:sup>([emim][ClO<jats:sub>4</jats:sub>],l) = +24 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and the associated standard absolute entropies, of the solid [emim][ClO<jats:sub>4</jats:sub>], <jats:italic>S</jats:italic>°<jats:sub>298</jats:sub>([emim][ClO<jats:sub>4</jats:sub>],s) = 83 ± 4 cal<jats:bold>·</jats:bold>K<jats:sup>–1</jats:sup><jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup>. The following combustion and detonation parameters are assigned to [emim][ClO<jats:sub>4</jats:sub>] in its (ionic) liquid form: specific impulse (<jats:italic>I</jats:italic><jats:sub>sp</jats:sub>) = 228 s (monopropellant), detonation velocity (<jats:italic>V</jats:italic><jats:sub>oD</jats:sub>) = 5466 m<jats:bold>·</jats:bold>s<jats:sup>–1</jats:sup>, detonation pressure (<jats:italic>p</jats:italic><jats:sub>C–J</jats:sub>) = 99 kbar, explosion temperature (<jats:italic>T</jats:italic><jats:sub>ex</jats:sub>) = 2842 K.</jats:p>
  • Beschreibung: <jats:title>Abstract</jats:title><jats:p>This paper estimates some thermochemical (in kcal mol<jats:sup>–1</jats:sup>) and detonation parameters for the ionic liquid, [emim][ClO<jats:sub>4</jats:sub>] and its associated solid in view of its investigation as an energetic material. The thermochemical values estimated, employing CBS‐4M computational methodology and volume‐based thermodynamics (VBT) include: lattice energy, <jats:italic>U</jats:italic><jats:sub>POT</jats:sub>([emim][ClO<jats:sub>4</jats:sub>]) ≈︁ 123 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup>; enthalpy of formation of the gaseous cation, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic>°([emim]<jats:sup>+</jats:sup>, g) = 144.2 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and anion, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic>°([ClO<jats:sub>4</jats:sub>]<jats:sup>–</jats:sup>, g) = –66.1 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup>; the enthalpy of formation of the solid salt, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic>°([emim][ClO<jats:sub>4</jats:sub>],s) ≈︁ –55 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and for the associated ionic liquid, Δ<jats:sub>f</jats:sub><jats:italic>H</jats:italic><jats:sup>o</jats:sup>([emim][ClO<jats:sub>4</jats:sub>],l) = –52 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> as well as the corresponding Gibbs energy terms: Δ<jats:sub>f</jats:sub><jats:italic>G</jats:italic>°([emim][ClO<jats:sub>4</jats:sub>],s) ≈︁ +29 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and Δ<jats:sub>f</jats:sub><jats:italic>G</jats:italic><jats:sup>o</jats:sup>([emim][ClO<jats:sub>4</jats:sub>],l) = +24 ± 16 kcal<jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup> and the associated standard absolute entropies, of the solid [emim][ClO<jats:sub>4</jats:sub>], <jats:italic>S</jats:italic>°<jats:sub>298</jats:sub>([emim][ClO<jats:sub>4</jats:sub>],s) = 83 ± 4 cal<jats:bold>·</jats:bold>K<jats:sup>–1</jats:sup><jats:bold>·</jats:bold>mol<jats:sup>–1</jats:sup>. The following combustion and detonation parameters are assigned to [emim][ClO<jats:sub>4</jats:sub>] in its (ionic) liquid form: specific impulse (<jats:italic>I</jats:italic><jats:sub>sp</jats:sub>) = 228 s (monopropellant), detonation velocity (<jats:italic>V</jats:italic><jats:sub>oD</jats:sub>) = 5466 m<jats:bold>·</jats:bold>s<jats:sup>–1</jats:sup>, detonation pressure (<jats:italic>p</jats:italic><jats:sub>C–J</jats:sub>) = 99 kbar, explosion temperature (<jats:italic>T</jats:italic><jats:sub>ex</jats:sub>) = 2842 K.</jats:p>
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