Experimental and Computational Investigation of the Energetics of the Three Isomers of Monochloroaniline

Silva, Manuel A. V. Ribeiro Da; Gomes, José R. B.; Ferreira, Ana I.M.C. Lobo

doi:10.1021/jp0519565

Cited by 43 publications

(47 citation statements)

References 59 publications

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“…Values of D f H m ðgÞ were also estimated for isomers of chloronitroaniline using the values of standard molar enthalpies of formation in gaseous state of 3-and 4-chloroaniline, by means of the following approach: chloroaniline + nitroaniline À aniline, considering the values of D f H m ðgÞ for 2-chloroaniline (53.4 ± 3.1) kJ AE mol À1 [9], 3-chloroaniline (53.0 ± 2.8) kJ AE mol À1 [9], 4-chloroaniline (59.7 ± 2.3) kJ AE mol À1 [9], and aniline (87.1 ± 1.1) kJ AE mol À1 [43], being also registered in table 9 (approach II). …”

Section: Enthalpies Estimated With the Cox Schemementioning

confidence: 99%

“…The present work is part of our broad interest on the thermochemistry of halogenated anilines, for which we have studied fluoroanilines [6,7], chloroanilines [8][9][10][11], bromoanilines [12], and iodoanilines [13]. Recently, two isomers of chloronitroaniline, 2-chloro-4-nitroaniline and 2-chloro-5-nitroaniline, were the object of a detailed experimental and computational study [14].…”

Section: Introductionmentioning

confidence: 99%

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Combined experimental and computational thermochemistry of isomers of chloronitroanilines

Silva

Lima

Moreno

et al. 2008

The Journal of Chemical Thermodynamics

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Section: Enthalpies Estimated With the Cox Schemementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Combined experimental and computational thermochemistry of isomers of chloronitroanilines

Silva

Lima

Moreno

et al. 2008

The Journal of Chemical Thermodynamics

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“…32 Vibrational frequencies have also been calculated at the same level of theory used in the optimization procedure. This is used to correct the computed electronic energy values for Zero-Point Energies, ZPE, as well as translational, rotational, and vibrational contributions to the enthalpy at T ¼ 298:15 K. The above mentioned exchange-correlation functional was chosen since, in previous works devoted to the thermochemistry of halogenated anilines, 10,[33][34][35] it was found that the use of this functional permitted estimation of accurate gas-phase enthalpies of formation for this class of compounds. Atoms in Molecules calculations have been performed by means of the TOPMOD code.…”

mentioning

confidence: 99%

Experimental and Computational Study on the Thermochemistry of Bromoanilines

Silva¹,

Ferreira²,

Gomes³

2006

Bulletin of the Chemical Society of Japan

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The standard (p ¼ 0:1 MPa) molar enthalpies of formation of 2-, 3-, and 4-bromoaniline, 2,4-, 2,5-, and 2,6-dibromoaniline, and 2,4,6-tribromoaniline were derived from the standard molar enthalpies of combustion, in oxygen, which yields CO 2 (g), N 2 (g), and HBr Á 600H 2 O(l), at T ¼ 298:15 K, measured by using rotating-bomb calorimetry.The standard molar enthalpies of sublimation, or vaporization, of these compounds at T ¼ 298:15 K were measured by using Calvet microcalorimetry, and so their standard molar enthalpies of formation in the gaseous state were derived. The enthalpies of fusion of the solid compounds were determined by DSC. The gas-phase enthalpies of formation were also estimated by density functional theory calculations performed at the BP86/6-31+G Ã level. As a result it is confirmed that thermodynamic data is consistent with intramolecular N-HÁÁÁBr hydrogen bonding.Aromatic amines are of great importance in biological and material sciences as well as in pharmaceutical and chemical industries. Halogenated anilines have gained the most focus of all of the aromatic amines, due to their high toxicity and wide uses. For example, they may be used as reagents or precursors for synthesizing organic dyes, in pigments, in agricultural agents, in pharmaceuticals and in the rubber industries.1,2 Haloanilines are frequently found in both effluents of waste water treatment plants and surface water, due to chemical degradation or biotransformation of pesticides and herbicides, or due to accidental spills and illegal release of industrial and municipal wastewater. 3 These compounds have been determined to induce several kinds of toxicity, like methemoglobinemia, splenotoxicity, hepatotoxicity, and nephrotoxicity. 2,4Because of their stability in the presence of air and humidity, and potentially attractive economics, 5,6 aniline and haloanilines have been also used in the synthesis of conducting polymers with applications in rechargeable batteries, electromagnetic interference shielding, electrochromic display devices, sensors, and electrocatalysis.The current work presents the results of calorimetric and computational thermochemistry studies on bromoanilines. The experimental investigation includes the determination of the standard massic energies of combustion in oxygen at T ¼ 298:15 K of the different bromoanilines using a rotatingbomb combustion calorimeter, from which the values of the standard molar enthalpies of formation in the condensed phase were derived. The determination of the standard molar enthalpies of sublimation or vaporization at T ¼ 298:15 K was done by using Calvet microcalorimetry with the high-temperature vacuum sublimation technique; these values allowed the derivation of the standard molar enthalpies of formation, in the gaseous state, of 2-, 3-, and 4-bromoaniline, 2,4-, 2,5-, and 2,6-dibromoaniline, and 2,4,6-tribromoaniline, which were compared with values estimated by the Cox scheme 7 and those obtained by density functional theory calculations. Experimental Materials.The three mono...

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“…Chlorinated aromatic compounds, as such chlorophenols [1], chloroanilines [2][3][4][5], chloronitroanilines [6] and chloropyridines [7], are among the classes of compounds that we have been investigating, since they can have a very high environmental impact.…”

Section: Introductionmentioning

confidence: 99%