Ribeiro da Silva Manuel A V, Gomes José R B, Ferreira Ana I M C L
Centro de Investigação em Química, Departamento de Química, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal.
J Phys Chem B. 2005 Jul 14;109(27):13356-62. doi: 10.1021/jp0519565.
The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 +/- 3.1 kJ.mol(-1) for 2-chloroaniline, 53.0 +/- 2.8 kJ.mol(-1) for 3-chloroaniline, and 59.7 +/- 2.3 kJ.mol(-1) for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N-H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters.
通过旋转弹燃烧量热法测量在T = 298.15 K时2-氯苯胺、3-氯苯胺和4-氯苯胺在氧气中的标准燃烧摩尔能量，由此推导出它们的标准（p° = 0.1 MPa）摩尔生成焓。采用卡尔维高温真空升华技术测量这三种异构体的汽化焓或升华焓。这两个热力学参数得出了气相中三种氯苯胺异构体在T = 298.15 K时的标准摩尔生成焓，2-氯苯胺为53.4 ± 3.1 kJ·mol⁻¹，3-氯苯胺为53.0 ± 2.8 kJ·mol⁻¹，4-氯苯胺为59.7 ± 2.3 kJ·mol⁻¹。这些修正了先前发表数据的值用于检验所使用的计算方法。据此，计算了气相酸度、质子亲和能、给电子能力和N - H键解离焓，发现与这些参数现有的实验数据比较吻合。
