Low-Temperature Heat Capacities and Derived Thermodynamic Functions of 1,4-Dichlorobenzene, 1,4-Dibromobenzene, 1,3,5-Trichlorobenzene, and 1,3,5-Tribromobenzene

Linde, Peter R. van der; Miltenburg, J.C. van; Berg, G.J.K. van den; Oonk, H. A. J.

doi:10.1021/je049762q

Cited by 22 publications

(13 citation statements)

References 27 publications

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“…Beyond these compilations a large number of recent papers presenting the heat-capacity data of several classes of compounds and of individual molecules of any kind as well as their temperature dependence have been published up to the present. Special mention shall be given to the hydrocarbons [49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65], halogenated hydrocarbons [66,67,68,69,70,71], unsubstituted and substituted alcohols and polyols including sugar derivatives [72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99,100,101,102,103,104,105,106,107], phenol derivatives [108,109], carboxylic acids […”

Section: Resultsmentioning

confidence: 99%

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at and around 298.15 K Based on Their “True” Molecular Volume

Naef

2019

Molecules

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A universally applicable method for the prediction of the isobaric heat capacities of the liquid and solid phase of molecules at 298.15 K is presented, derived from their “true” volume. The molecules’ “true” volume in A3 is calculated on the basis of their geometry-optimized structure and the Van-der-Waals radii of their constituting atoms by means of a fast numerical algorithm. Good linear correlations of the “true” volume of a large number of compounds encompassing all classes and sizes with their experimental liquid and solid heat capacities over a large range have been found, although noticeably distorted by intermolecular hydrogen-bond effects. To account for these effects, the total amount of 1303 compounds with known experimental liquid heat capacities has been subdivided into three subsets consisting of 1102 hydroxy-group-free compounds, 164 monoalcohols/monoacids, and 36 polyalcohols/polyacids. The standard deviations for Cp(liq,298) were 20.7 J/mol/K for the OH-free compunds, 22.91 J/mol/K for the monoalcohols/monoacids and 16.03 J/mol/K for the polyols/polyacids. Analogously, 797 compounds with known solid heat capacities have been separated into a subset of 555 OH-free compounds, 123 monoalcohols/monoacids and 119 polyols/polyacids. The standard deviations for Cp(sol,298) were calculated to 23.14 J/mol/K for the first, 21.62 J/mol/K for the second, and 19.75 J/mol/K for the last subset. A discussion of structural and intermolecular effects influencing the heat capacities as well as of some special classes, in particular hydrocarbons, ionic liquids, siloxanes and metallocenes, has been given. In addition, the present method has successfully been extended to enable the prediction of the temperature dependence of the solid and liquid heat capacities in the range between 250 and 350 K.

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Section: Resultsmentioning

confidence: 99%

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at and around 298.15 K Based on Their “True” Molecular Volume

Naef

2019

Molecules

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“… a The value is calculated as the sum S m ° (g, 298 K) G3MP2 = 346.6 J·K –1 ·mol –1 and the contribution R × ln σ for the symmetry number (σ = 6); b The value is calculated from the experimental S m ° (cr, 298 K) = 174.0 J·K –1 ·mol –1 and the sublimation entropy Δ cr g S m ° = 166.4 J·K –1 ·mol –1 derived from the vapor pressure measurements between 273.5 and 303.5 K (see Table S3). …”

Section: Discussionmentioning

confidence: 99%

“… b The value is calculated from the experimental S m ° (cr, 298 K) = 174.0 J·K –1 ·mol –1 and the sublimation entropy Δ cr g S m ° = 166.4 J·K –1 ·mol –1 derived from the vapor pressure measurements between 273.5 and 303.5 K (see Table S3). …”

Section: Discussionmentioning

confidence: 99%

“… a Calculated by eq . b Calculated by eq . c From Tables and . d From Table S4. e The value is calculated from the experimental S m ° (cr, 298 K) = 174.0 J·K –1 ·mol –1 and the entropy of fusion Δ cr 1 S m ° = 55.8 J·K –1 ·mol –1 …”

Section: Discussionmentioning

confidence: 99%

“… e The value is calculated from the experimental S m ° (cr, 298 K) = 174.0 J·K –1 ·mol –1 and the entropy of fusion Δ cr 1 S m ° = 55.8 J·K –1 ·mol –1 …”

Section: Discussionmentioning

confidence: 99%

See 2 more Smart Citations

Thermodynamic Analysis of Isomerization Equilibria of Chlorotoluenes and Dichlorobenzenes in a Biphasic Reaction Systems Containing Highly Acidic Chloroaluminate Melts

et al. 2016

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Thermodynamics and kinetics of the isomerization of chlorotoluenes and dichlorobenzene to the technically desired meta-isomers have been studied in the presence of highly acidic chloroaluminate melts with alkali metal and organic imidazolium cations. Enthalpies of four isomerization processes in reacting systems of chlorotoluenes and dichlorobenzene were obtained from temperature dependencies of the corresponding equilibrium constants in the liquid phase. Experimental reaction enthalpies, enthalpies of vaporization, and absolute vapor pressures of chlorotoluenes and dichlorobenzene have been used for the validation of quantum-chemical methods to predict thermodynamic functions of the four reactions under study successfully. Values of the standard Gibbs energies of formation, standard enthalpies and entropies of formation of chlorotoluenes and dichlorobenzenes in the liquid and in the gas phase have been derived. These values allow optimization of liquid-liquid biphasic manufacturing technologies for halogen-substituted benzenes.

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Aromatics

Linde

Oonk

2021

Physical Chemistry in Action

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Low-Temperature Heat Capacities and Derived Thermodynamic Functions of 1,4-Dichlorobenzene, 1,4-Dibromobenzene, 1,3,5-Trichlorobenzene, and 1,3,5-Tribromobenzene

Cited by 22 publications

References 27 publications

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at and around 298.15 K Based on Their “True” Molecular Volume

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at and around 298.15 K Based on Their “True” Molecular Volume

Thermodynamic Analysis of Isomerization Equilibria of Chlorotoluenes and Dichlorobenzenes in a Biphasic Reaction Systems Containing Highly Acidic Chloroaluminate Melts

Aromatics

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