Estimation of &amp;Delta;<sub>f</sub>of nitro derivatives of benzene and toluene using AM1 and DSC

Hwang, Dong-Rong; Tamura, Masamitsu; Yoshida, Tadao; Tanaka, Nariaki; Hosoya, Fumio

doi:10.1080/07370659008017247

Cited by 21 publications

(2 citation statements)

References 6 publications

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“…It should be noted that an examination of closely related species provides additional evidence of a possible small error in the experimental enthalpies of formation of 16, 21, 23, 28, 31, 33, 55, 57, 65, 71−73, 77, and 95. Of a series nitrophenols (24−26, 31−33), dichoronitrobenzenes (62−65), and chloronitrophenols (69− 71), the marked difference between the computed and experimental enthalpies of formation is found only for two nitrophenols (31,33), one dichloronitrobenzene (65), and one chloronitrophenol (71), whereas the difference between calculated and experimental values does not exceed 2.2 kJ• mol −1 for the remaining nine compounds.…”

Section: Resultsmentioning

confidence: 97%

Use of G4 Theory for the Assessment of Inaccuracies in Experimental Enthalpies of Formation of Aromatic Nitro Compounds

Suntsova

Дорофеева

2015

J. Chem. Eng. Data

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The gas-phase enthalpies of formation (Δ f H 298 °) of 101 aromatic nitro compounds were calculated using the Gaussian-4 (G4) theory applied to the atomization and isodesmic reaction energies. The Δ f H 298 °(g) values calculated from the atomization reactions were underestimated by an average of 13 kJ•mol −1 and they could not be used for the assessment of inaccuracies in the experimental enthalpies of formation. A good agreement with the most available experimental data was obtained using the isodesmic reaction procedure. From 5 to 26 isodesmic reactions with different reference species were constructed for each compound. About 15 aliphatic nitro compounds and 100 different C/H/N/O/Cl compounds were used as the reference species in these reactions; the accuracy of enthalpies of formation of all reference compounds was preliminarily confirmed by theoretical calculations. Evidence of accuracy of experimental data was provided by the agreement with calculated values. The differences between the calculated and the experimental enthalpies of formation in the range from (8 to 46) kJ•mol −1 were assigned to possible errors in the experimental values for 21 compounds. The theoretical Δ f H 298 °(g) values were recommended for these compounds as being more reliable than the experimental values. On the basis of theoretical results, a reference data set of internally consistent gas-phase enthalpies of formation of aromatic nitro compounds was provided. Both experimental and calculated values are included in this data set. The recommended Δ f H 298 °(g) values of aromatic nitro compounds are consistent with each other and with Δ f H 298 °(g) values of about 115 different C/H/N/O/Cl compounds including aliphatic nitro compounds. More accurate condensed phase enthalpies of formation and enthalpies of sublimation (or vaporization) were recommended in some cases based on a critical analysis of reported experimental data supplemented by quantum chemical calculations.

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Section: Resultsmentioning

confidence: 97%

Use of G4 Theory for the Assessment of Inaccuracies in Experimental Enthalpies of Formation of Aromatic Nitro Compounds

Suntsova

Дорофеева

2015

J. Chem. Eng. Data

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“…In 1990, Hwang et al reported a melting point for TNT of 352 K (79 °C) with a melting enthalpy of DfusH = 5.8 kcal mol -1 (24.27 kJ mol -1 ; 106.84 J g -1 ) [20] . The authors also determined the heat of vaporization DvapH = 19.5 kcal mol -1 (81.59 kJ mol -1 ) at a boiling point of 202°C and a heat of sublimation of DsubH = 25.1 kcal mol -1 (105.02 kJ mol -1 ; 462.36 J g -1 ) [20]. In the same year, Hu et al found a melting point for TNT of Tfus = 80.6°C (353.75 K) with a melting enthalpy of DfusH = 22.41 kJ mol -1 (98.66 J g -1 ) [21].…”

Section: Crystallographic Datamentioning

confidence: 99%

Topological pressure-temperature state diagram of the crystalline dimorphism of 2,4,6-trinitrotoluene

Céolin

Rietveld

2020

Fluid Phase Equilibria

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The phase behavior of explosive substances is important for the proper design of stable explosive devices. However, the equilibrium behavior of chemical compounds can be difficult to assess, because thermodynamic and kinetic behaviors are generally convoluted in the experimental results. The phase behavior of TNT is a case in point. A thorough review of the literature data demonstrates that the orthorhombic polymorph is the most stable under ambient conditions. Using the topological approach for the construction of a pressure-temperature phase diagram, it can be shown that all data is consistent with an overall enantiotropic system. Nonetheless, it is also clear that the differences between the orthorhombic and the monoclinic polymorphs are relatively small and that the driving force of interconversion between the two under ambient conditions is therefore limited.

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Density Functional Calculations on the Heats of Formation of Certain Aromatic Nitro Compounds

Chen¹,

Chieh²

2002

J Chinese Chemical Soc

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In order to select suitable isodesmic reactions, heats of formation at 298 K of seven aromatic nitro compounds were calculated by various density functional theories, together with different basis sets. The calculated heats of formation for nitrobenzene, 1,2‐dinitrobenzene, 1,3‐dinitrobenzene, 1,4‐dinitrobenzene, 1,3,5‐trinitrobenzene, 1,2,3‐trinitrobenzene, and 1,2,4‐trinitrobenzene by various DFT methods were averaged to be 14.84, 23.23, 12.84, 12.89, 14.71, 30.61, and 25.73 kcal/mol, respectively. These values are very close to the experimental or multivariable linear regression results.

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Estimation of Δ_fof nitro derivatives of benzene and toluene using AM1 and DSC

Cited by 21 publications

References 6 publications

Use of G4 Theory for the Assessment of Inaccuracies in Experimental Enthalpies of Formation of Aromatic Nitro Compounds

Use of G4 Theory for the Assessment of Inaccuracies in Experimental Enthalpies of Formation of Aromatic Nitro Compounds

Topological pressure-temperature state diagram of the crystalline dimorphism of 2,4,6-trinitrotoluene

Density Functional Calculations on the Heats of Formation of Certain Aromatic Nitro Compounds

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Estimation of &Delta;fof nitro derivatives of benzene and toluene using AM1 and DSC

Cited by 21 publications

References 6 publications

Use of G4 Theory for the Assessment of Inaccuracies in Experimental Enthalpies of Formation of Aromatic Nitro Compounds

Use of G4 Theory for the Assessment of Inaccuracies in Experimental Enthalpies of Formation of Aromatic Nitro Compounds

Topological pressure-temperature state diagram of the crystalline dimorphism of 2,4,6-trinitrotoluene

Density Functional Calculations on the Heats of Formation of Certain Aromatic Nitro Compounds

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Estimation of Δ_fof nitro derivatives of benzene and toluene using AM1 and DSC