Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water

Reschke, Thomas; Zherikova, Kseniya V.; Verevkin, Sergey P.; Held, Christoph

doi:10.1016/j.xphs.2015.12.020

Cited by 38 publications

(32 citation statements)

References 57 publications

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“…This work complements our previous studies of the thermodynamic properties of amides and benzoic acid derivatives . We have performed experimental and computational studies of the substituted benzamides presented in Figure .…”

Section: Introductionsupporting

confidence: 52%

“…These experimental values can be used now for comparison with theoretical values calculated by any of the available high‐level quantum‐chemical methods. The high‐level composite methods have been successfully used for substituted benzamides in our recent work . A disagreement or agreement between the experimental and theoretical

Δ_{normalf} H_{m}^{\circ}

(g, 298.15 K) values could provide a criterion for the mutual validation for both results.…”

Section: Resultsmentioning

confidence: 99%

“…It is clear that the R-substituted benzamides studied in this work are ap arentt ot he familyo fR -substitutedb enzoic acids (see Figure 3) and both families are expected to exhibit comparable regularities in their thermochemical properties:t he vaporization enthalpies and the gas-phase enthalpies of formation. As am atter of fact, thesethermochemical properties for substituted benzoic acids have been evaluated just recently [5][6][7][8][9][10][11] and they have been shown to be highly internally consistent. First, we correlated the enthalpies of vaporization of pairs of similarly shaped molecules, for example, 4-nitrobenzamide and 4-nitrobenzoic acid.…”

Section: Correlation Of Vaporization Enthalpieso Fr -Substituted Benzmentioning

confidence: 99%

“…This work complements our previouss tudies of the thermodynamic properties of amides and benzoic acid derivatives. [5][6][7][8][9][10][11][12][13] We have performed experimental and computational studies of the substituted benzamides presented in Figure 2. To perform structure-property analysis, the availablet hermochemical data for similarly structured benzamides and benzoica cidd erivatives substituted with various substituents in the ortho-, meta-, and para-positions on the benzene ring.…”

Section: Introductionmentioning

confidence: 99%

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Thermochemistry of Substituted Benzamides and Substituted Benzoic Acids: Like Tree, Like Fruit?

2018

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Structure-property analyses of thermodynamic properties in chemical families of R-substituted benzamides, R-substituted benzoic acids, as well as R-substituted benzenes have been performed. The general linear interrelations for the vaporization enthalpies and the gas-phase enthalpies of formation between the chemical families under study have been established. These linear correlations provide a simple method for prediction of thermodynamic properties for benzenes with various combination of R-group substituents on the benzene ring. In addition, the robust structure-property correlations revealed in this study can serve for the establishment of the internal consistency of experimental results available for each chemical series.

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Section: Introductionsupporting

confidence: 52%

Δ_{normalf} H_{m}^{\circ}

(g, 298.15 K) values could provide a criterion for the mutual validation for both results.…”

Section: Resultsmentioning

confidence: 99%

Section: Correlation Of Vaporization Enthalpieso Fr -Substituted Benzmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermochemistry of Substituted Benzamides and Substituted Benzoic Acids: Like Tree, Like Fruit?

2018

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“…All monohalobenzoic acids are solid compounds at ambient conditions with melting temperatures in the range T 5 396-544 K. Enthalpies of sublimation D g cr H m for these compounds at various temperatures have been determined calorimetrically with a Tian-Calvet microcalorimeter equipped with a Knudsen cell (C) [121][122][123] and with the ''vacuumsublimation drop-calorimetric (DC) method,'' 83,124 as well as indirectly through the determination of the temperature dependence of sublimation pressures measured by the Knudsen effusion (K) 125,126 or transpiration (T) method. 79,[127][128][129][130] Enthalpies of sublimation with remarkably small relative uncertainties (less than 1%) were also reported by Holdiness 131 based on sublimation from a cell in a differential scanning calorimeter (DSC), using a method developed by Beech and Lintonbon. 132 Beech and Lintonbon estimated a relative uncertainty of 15% for their method, which is in accord with the very large deviations of results reported by Holdiness 131 from all others.…”

Section: Experimental Sources Of Enthalpies Of Sublimationmentioning

confidence: 72%

Critical Evaluation of Thermodynamic Properties for Halobenzoic Acids Through Consistency Analyses for Results from Experiment and Computational Chemistry

Chirico

Kazakov

Bazyleva

et al. 2017

Journal of Physical and Chemical Reference Data

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Thermodynamic properties of the twelve monohalobenzoic acids are critically evaluated through the application of computational chemistry methods for the ideal-gas phase and thermodynamic consistency assessment of properties determined experimentally and reported in the literature, including enthalpies of combustion, enthalpies of sublimation, and enthalpies of fusion. The compounds of interest are the 2-, 3-, and 4-halo isomers of fluoro-, chloro-, bromo-, and iodobenzoic acids. Computations were validated by comparison with critically evaluated entropies and heat capacities in the ideal-gas state for benzoic acid, benzene, and some halobenzenes. Experimental enthalpies of formation for 2-and 3-bromobenzoic acids, measured by well-established research groups, are mutually inconsistent and further, are shown to be inconsistent with the computations and assessment in this work. Origins of the discrepancies are unknown, and recommended values for these compounds are based on computations and enthalpies of sublimation validated, in part, by a structure-property (i.e., group-additivity) analysis. Lesser, but significant, inconsistencies between experimental and computed results are demonstrated also for 3-and 4-iodobenzoic acids. The comparison of enthalpies of formation based on the experiment and computation for the ideal-gas state of 1-and 2-chloro-, bromo-, and iodonaphthalenes provides additional support for the findings for halobenzoic acids and also reveals some anomalous results in the experimental literature for chloronaphthalenes. Computations are discussed in detail to demonstrate the approach required to obtain optimal results with modern quantum chemical methods.

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Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

et al. 2020

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Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non‐innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT‐IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ‐nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa‐substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non‐innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained.

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Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water

Cited by 38 publications

References 57 publications

Thermochemistry of Substituted Benzamides and Substituted Benzoic Acids: Like Tree, Like Fruit?

Thermochemistry of Substituted Benzamides and Substituted Benzoic Acids: Like Tree, Like Fruit?

Critical Evaluation of Thermodynamic Properties for Halobenzoic Acids Through Consistency Analyses for Results from Experiment and Computational Chemistry

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

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