Thermodynamic properties of molecular organic crystals containing nitrogen, oxygen and sulfur. III. Molar heat capacities measured by differential scanning calorimetry

Wit, H. G. M. de; Offringa, J. C. A.; Kruif, C. G. de; Miltenburg, J.C. van

doi:10.1016/0040-6031(83)80006-9

Cited by 24 publications

(14 citation statements)

References 7 publications

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“…The only thermodynamic property which is known from experiment is the specific heat of squaric acid. [89][90]30 The experimental and computed values at 315 K ( =121.6 J • K −1 • mol −1 and =115.6 J • K −1 • mol −1 , respectively) agree satisfactorily, the values differing by about 4.9%. The calculated specific heats of deltic and croconic acids at the highest temperature considered in the present work (1000 K), 166.6 and 249.6 J • K −1 • mol −1 , respectively, are 16 The expected accuracy for the computed isobaric specific heats and entropies given in Table 1 may be assessed from the analysis of the previous results obtained using the same methodology for materials in which the corresponding experimental values are available.…”

Section: Results and Discusionmentioning

confidence: 56%

“…The only thermodynamic property which is known from experiment is the specific heat of squaric acid. 89,90,30 The experimental and computed values at 315 K (C p exp = 121.6 J K −1 mol −1 and C p calc = 115.6 J K −1 mol −1 ) agree satisfactorily, with the values differing by about 4.9%. The calculated specific heats of deltic and croconic acids at the highest temperature considered in the present work (1000 K), 166.6 and 249.6 J K −1 mol −1 , respectively, are 16.5 and 16.6% below the corresponding Dulong− Petit asymptotic limits (199.5 and 299.3 J K −1 mol −1 ).…”

Section: Theorymentioning

confidence: 80%

See 1 more Smart Citation

Thermodynamic, Raman Spectroscopic, and UV–Visible Optical Characterization of the Deltic, Squaric, and Croconic Cyclic Oxocarbon Acids

Colmenero

Escribano

2019

J. Phys. Chem. A

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A precise and complete thermodynamic, Raman spectroscopic and ultraviolet-visible optical characterization of the deltic, squaric and croconic cyclic oxocarbon acids is obtained using theoretical solid-state methods employing very demanding calculation parameters. The computed fundamental thermodynamic properties include the isobaric specific heat, the entropy, the enthalpy and the Gibbs free energy as a function of temperature. The calculated specific heats at 298.15 K of the deltic, squaric and croconic acids are 89.7, 111.2 and 133.2 J • mol −1 • K −1 , respectively, and the corresponding entropies are 98.3, 117.3 and 136.5 J • mol −1 • K −1 . The only value of these properties known from experimental measurements is the specific heat of the squaric acid which differs from the computed value at 315 K by about 4.9%. The calculated values of the thermodynamic properties are then used to determine the thermodynamic properties of formation of these materials in terms of the elements. As an application of the calculated thermodynamic properties of formation, the Gibbs free energies of reaction and associated reaction constants are evaluated for the reactions of thermal decomposition and complete combustion of the squaric and croconic acids and the reaction of interconversion between them. The only available experimental values of these properties, namely the enthalpies of combustion of squaric and croconic acids at room temperature, are reproduced theoretically with high accuracy. The Raman spectra of these materials are also computed using Density Functional Perturbation Theory. The analysis of the theoretical Raman spectra of these materials points out to significant differences with respect to their usual empirical assignment. Therefore, the Raman spectra of these materials is fully reassigned. Finally, the ultraviolet-visible (UV-Vis) optical properties of the deltic, squaric and croconic acids are computed. The UV-Vis absorption spectrum of the croconic acid in the spectral region 225-425 nm and the UV absorption spectrum of the squaric acid in the region 200-350 nm which had previously been measured experimentally are well reproduced. The corresponding spectrum for the deltic acid and the reflectivity, optical conductivity, dielectric, refractive index and loss optical functions of the three materials, which had never been published as far as we know, are reported as a function of the wavelength of incident radiation in the range 200-750 nm. The origin of the peaks in the absorption spectra which had not been analyzed so far is unveiled here by examining the inter-band electronic transitions in these materials.their reactions of complete combustion:and the reaction of conversion between them in the presence of carbon monoxide: (E) H 2 C 4 O 4 (cr) + CO(g) → H 2 C 5 O 5 (cr) as a function of temperature. The thermodynamic parameters of organic compounds are extraordinarily important not only in

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Section: Results and Discusionmentioning

confidence: 56%

Section: Theorymentioning

confidence: 80%

Thermodynamic, Raman Spectroscopic, and UV–Visible Optical Characterization of the Deltic, Squaric, and Croconic Cyclic Oxocarbon Acids

Colmenero

Escribano

2019

J. Phys. Chem. A

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“…Our experimentally determined values for 1,3-dithiane, 55.9 8 8Ca nd 14.1 kJ mol À1 ,a re in good agreement with previous literature values of 54.1 8 8Ca nd 14.4 kJ mol À1 . [27] Them ixture exhibits ap hase behavior characterized by as ingle eutectic point and possesses an extended liquidus compositional region, ranging from approximately 35 mol % to 65 mol %o f1 ,3-dithiane,p resenting significant deviation from ideality on both sides of the phase diagram. Consideration of the melting behavior over the range of compositions (Figure 1b and Figures SI8-SI18) reveals two distinct melting endotherms:a pproximately 10 8 8Cf or 10 mol %t o6 0mol % 1,3-dithiane and 20 8 8Cfor 60 mol %to90mol %1,3-dithiane.…”

Section: Resultsmentioning

confidence: 99%

Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents

et al. 2021

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While research into deep eutectic solvents (DESs) has expanded over the previous two decades, the focus has remained on the utilization of hydrogen bond donors in these systems. Additionally, the majority of the known DESs rely on at least one ionic component. Through the combination of 1,3‐dithiane and 1,2‐diiodo‐3,4,5,6‐tetrafluorobenzene (1,2‐F4DIB), we report the first known DES based on halogen bonding. This mixture remains a liquid, with a eutectic melting temperature of 13.7 °C over a range of 1,3‐dithiane mole fraction (0.35 to 0.75). Additionally, cocrystals of 1,3‐ and 1,4‐dithiane with 1,2‐, 1,3‐, and 1,4‐F4DIB, as well as 1,3,5‐trifluoro‐2,4,6‐triiodobenzene were studied via single‐crystal X‐ray diffraction. These data reveal a wide range of halogen bonding strengths (0.85

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“…The drawn line in Fig. 4 represents the data we published in 1983 [4]. Between 100 and 380 K the molar heat capacity data can be represented within the a The temperature range, the stabilisation and input times and the mean heating rate are given.…”

Section: Adiabatic Measurementsmentioning

confidence: 99%

“…Vapour pressures and the derived enthalpy of vaporisation of 1,3,5-trithiane were published in 1983 [3]. Heat capacity measurements made by DSC on 1,3,5-trithiane were published in the temperature range between 300 and 450 K [4]. This work reports on the thermal properties of 1,3,5-trithiane between 15 K and the melt.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic properties of 1,3,5-trithiane derived from solid phase heat capacity measurements by adiabatic calorimetry and DSC measurements in the melting range

Miltenburg

Ekeren

2002

Thermochimica Acta

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The thermal properties of 1,3,5-trithiane were measured with adiabatic calorimetry and DSC between 15 and 500 K. It was necessary to purify the compound even as the stated purity of the commercial product was >99%. The impurity present triggers a reaction at the melting point. The absolute entropy at 298.15 K was measured to be (156:2 AE 0:8) J K À1 mol À1 , the enthalpy increment from 0 to 298.15 K is (22936 AE 100) J mol À1. The enthalpy of melting was found to be (32:2 AE 0:3) kJ mol À1 , the fusion temperature 488.4 K. The molar heat capacity of the solid between 100 and 380 K can be described by a polynomial function C p ¼ f24:17 þ 0:4004T À 9:9605:10, the standard deviation of this fit is 0.24 J K À1 mol À1. #

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Thermodynamic properties of molecular organic crystals containing nitrogen, oxygen and sulfur. III. Molar heat capacities measured by differential scanning calorimetry

Cited by 24 publications

References 7 publications

Thermodynamic, Raman Spectroscopic, and UV–Visible Optical Characterization of the Deltic, Squaric, and Croconic Cyclic Oxocarbon Acids

Thermodynamic, Raman Spectroscopic, and UV–Visible Optical Characterization of the Deltic, Squaric, and Croconic Cyclic Oxocarbon Acids

Halogen Bonding in Dithiane/Iodofluorobenzene Mixtures: A New Class of Hydrophobic Deep Eutectic Solvents

Thermodynamic properties of 1,3,5-trithiane derived from solid phase heat capacity measurements by adiabatic calorimetry and DSC measurements in the melting range

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