Thermochemistry of di-substituted benzenes: nitro- and dimethylamino benzaldehydes

doi:10.1016/j.jct.2020.106060

The Journal of Chemical Thermodynamics

Volume 143, April 2020, 106060

https://doi.org/10.1016/j.jct.2020.106060 Get rights and content

Highlights

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Vapour pressures of substituted benzaldehydes measured by transpiration.
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Enthalpies of formation were measured by combustion calorimetry.
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Phase transition enthalpies derived were derived and evaluated.
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G4 gaseous enthalpies of formation in agreement with experiment.
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A set of reliable thermodynamic properties was recommended.
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Group-additivity was developed for prediction of thermodynamic properties.

Abstract

Standard molar enthalpies of vaporization/sublimation of nitro and amino-substituted benzaldehydes were obtained from the temperature dependence of vapour pressure measured by the transpiration method. Enthalpies of fusion of these compounds were measured by using DSC. Solution enthalpies of nitro and amino-substituted benzaldehydes were measured by using a solution calorimeter. Available from literature primary experimental results on temperature dependences of vapour pressures have been collected and they have been treated uniformly in order to derive vaporization/sublimation enthalpies at the reference temperature 298.15 K. Standard molar enthalpies of formation of crystalline isomers of nitro-benzaldehydes were measured by using combustion calorimetry. Gas phase molar enthalpies of formation of substituted benzaldehydes were calculated by the high-level quantum-chemical G4 method and they were used for evaluation of available experimental results. A set of thermodynamic properties of substituted benzaldehydes was recommended as reliable reference properties for thermochemical calculations. Simple group-additivity procedures were developed for estimation of vaporization enthalpies, gas-phase, and liquid-phase enthalpies of formation of substituted benzenes.

Introduction

Thermochemistry of substituted benzaldehydes is in disarray. Smoothed data on vapour pressures of isomeric nitro-benzaldehydes can be found in compilations by Stull [1] and Stephenson and Malanowski [2]. Origin, method and sample purity for these data are questionable. Results from combustion experiments on the crystalline nitro- and amino-substituted benzaldehydes reported in the literature [3], [4], [5], [6] seem to agree for each isomer. However, the standard molar enthalpies of formation derived from these results do not meet expectation for a reasonable level, if they are compared to the parent substituted benzenes. This paper extends our previous studies [7], [8], [9], [10] on the systematic investigation of substituent effects on the benzene ring. In this paper we report determination of vapour pressures, vaporization/sublimation enthalpies, fusion enthalpies, and enthalpies of formation of a series of ortho-, meta-, and para-nitro-benzaldehydes, as well as for ortho-, meta-, and para-N,N-dimethylamino-benzaldehydes (see Fig. 1). We used our new experimental results together with the data already available from the literature to obtain consistent data sets on phase transition enthalpies, as well as condensed- and gas-phase enthalpies of formation. The evaluated experimental data were useful for development of group-contributions being necessary for prediction of thermochemical properties of substituted benzenes.

Section snippets

Materials

Samples of 2-, 3-, and 4-nitro-benzaldehydes, as well as of 4-N,N-dimethylamino-benzaldehyde of 0.98–0.99 mass fraction (as stated by the manufacturer) were of commercial origin (see Table 1). Solid samples of substituted benzaldehydes were additionally purified by the fractional sublimation in vacuum. No impurities (greater than 0.0004 mass fraction) were detected in samples used for thermochemical measurements. The degree of purity was determined using a GC equipped with a FID. A capillary

Vapour pressures

Temperature dependences of vapour pressures p_i for the substituted benzaldehydes measured in this work by the transpiration (see Table 2) were approximated with following equation [11]: $R \ln (p_{i} {/ p}_{r e f}) = a + \frac{b}{T} + Δ_{l, c r}^{g} C_{p, m}^{o} l n (\frac{T}{T_{0}})$

In this equation: $Δ_{l, c r}^{g} C_{p, m}^{o}$ is the difference between the molar heat capacities of the condensed (liquid or crystal) and gas phases; T₀ = 298.15 K was adopted in this work; $p_{r e f} = 1 Pa,$ R = 8.31446 J·K⁻¹·mol⁻¹ [13], a and b are adjustable parameters. Values of $Δ_{l, c r}^{g} C_{p, m}^{o}$ were

Conclusions

Vapour pressures and vaporization/sublimation enthalpies of nitro and amino substituted benzaldehydes were measured by the transpiration method. Enthalpies of fusion of these compounds were measured by using DSC. Standard molar enthalpies of formation of 2-, 3-, and 4-nitrobenzaldehydes were measured by the combustion calorimetry. The consistent set of vapour pressures, standard molar enthalpies of vaporization/sublimation, standard molar enthalpies of fusion, and standard molar enthalpies of

CRediT authorship contribution statement

Riko Siewert: Investigation, Validation, Formal analysis, Writing - review & editing. Aizat A. Samatov: Investigation, Validation, Writing - review & editing. Ruslan N. Nagrimanov: Investigation, Validation, Formal analysis, Writing - review & editing. Sergey P. Verevkin: Conceptualization, Methodology, Writing - original draft, Supervision.

Acknowledgments

This work has been supported by the German Science Foundation (DFG) in the frame of the priority program SPP 1708 “Material Synthesis Near Room Temperature” (grant VE 265-14/1 to SPV). This work has been partly supported by the Russian Government Program of Competitive Growth of Kazan Federal University.

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Thermochemistry of di-substituted benzenes: nitro- and dimethylamino benzaldehydes

Highlights

Abstract

Introduction

Section snippets

Materials

Vapour pressures

Conclusions

CRediT authorship contribution statement

Acknowledgments

J. Chem. Thermodyn.

Fluid Phase Equilib.

Thermochim. Acta

Thermochim. Acta

Thermochim. Acta

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Thermochim. Acta

Mater. Lett.

Chemosphere

J. Chem. Thermodyn.

Vapor pressure of pure substances. Organic and inorganic compounds

Ind. Eng. Chem. 39

Handbook of the Thermodynamics of Organic Compounds

The heats of combustion and formation of aromatic nitro compounds

J. Am. Chem. Soc.

Structure and reactivity of nitriles. Condensation reaction of phenylacetonitrile with benzaldehydes

Rev. Chim. (Bucharest)

Structure and reactivity of nitriles. II. Condensing reactions of methyl and dimethylphenylacetonitriles with substituted aromatic aldehydes

Rev. Chim. (Bucharest)

Heats of combustion of some organic nitrogen compounds

Ind. Eng. Chem.

Vapor pressures, enthalpies of vaporization and limiting activity coefficients in water at 100°C of 2-Furanaldehyde, Benzaldehyde, Phenylethanal and 2-Phenylethanol

J. Chem. Eng. Data

Thermodynamic study of pure methyl-benzaldehydes and their mixtures with ionic liquids, Vestnik (Herald) of St

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