Thermodynamic properties of sublimation of the ortho and meta isomers of acetoxy and acetamido benzoic acids

https://doi.org/10.1016/j.jct.2015.02.010Get rights and content

Highlights

  • Vapour pressures of ortho and meta acetoxy and acetamido benzoic acids are reported.

  • Results of temperatures and enthalpies of fusion are presented.

  • Standard molar ΔH, ΔS and ΔG of sublimation were derived.

  • Correlations for estimating vapour pressures are presented.

Abstract

This paper reports vapour pressures measured at several different temperatures using the Knudsen effusion method of ortho-acetoxybenzoic acid (aspirin) (341.1 to 361.1) K, meta-acetoxybenzoic acid (344.2 to 362.2) K, ortho-acetamidobenzoic acid (367.2 to 389.2) K, and meta-acetamidobenzoic acid (423.2 to 441.1) K. The experimental results enabled the determination of the standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, of the four compounds studied. DSC experiments yield results of the temperature and enthalpy of fusion. The experimental results were compared with literature ones for the para isomers of the acids acetoxybenzoic and acetamidobenzoic. Correlations involving temperature of fusion, and standard molar enthalpy and Gibbs energy of sublimation of several substituted benzoic acids were proposed. Those correlation equations allow a good estimative of volatility of benzoic acid derivatives from their enthalpies of sublimation and temperatures of fusion.

Introduction

Experimental results of thermodynamic properties of sublimation of several substituted benzoic acids and of some of their parent methyl esters have been reported by our research group [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12]. In this work these studies are extended to the ortho and meta isomers of acetoxy and acetamido benzoic acids enabling the comparison of the derived results with those reported before for the respective para isomers [7]. Moreover, we wanted to verify if a correlation relating temperatures of fusion, standard molar enthalpies and standard Gibbs energy of sublimation, derived previously for para-substituted benzoic acids [7], still hold for ortho and meta isomers. Ortho-acetoxybenzoic acid, also known as acetylsalicylic acid or aspirin, is one of the most widely used nonsteroidal anti-inflammatory drugs (NSAIDs) and its therapeutic properties have been discussed in the literature. Aspirin is often used as an antipyretic, analgesic and anti-inflammatory medication [13]. Durable use and high doses of this salicylate medication raise the risk of gastrointestinal complications; nevertheless, the ingestion of small daily doses has the potential to reduce repeated vascular events [14]. Both ortho and meta isomers of acetoxybenzoic acid are ligands of two novel organoantimony(V) and two organobismuth(V) complexes that exhibited antileishmanial and antibacterial activities [15]. The ortho isomer of acetamidobenzoic acid (N-acetylanthranilic acid) is a triboluminescent material [16], [17] and presents antimicrobial activity against some plant pathogen – antifungal activity against Fusarium avenaceum, Fusarium graminearum and Fusarium culmorum, and also antibacterial activity against Staphylococcus aureus and Escherichia coli [18]. Further, this compound is an intermediate degradation product of quinaldine in Arthrobacter sp., being metabolised to anthranilic acid [19], [20]. Representations of structures of the compounds studied in this work are presented in figure 1.

Section snippets

Materials and purity control

Table 1 reports analysis and purification details of the four compounds studied in this work: ortho-acetoxybenzoic acid (C9H8O4, CASNR 50-78-2), meta-acetoxybenzoic acid (C9H8O4, CASNR 6304-89-8), ortho-acetamidobenzoic acid (C9H9NO3, CASNR 89-52-1) and meta-acetamidobenzoic acid (C9H9NO3, CASNR 587-48-4). Prior to the experimental study, the purity of the samples was analysed by gas–liquid chromatography performed using an apparatus Agilent 4890D equipped with an HP-5 column (cross-linked,

Temperature, enthalpy and entropy of fusion

Table 2 presents the values of molar enthalpy, entropy, and temperature of fusion derived from DSC analysis of the four compounds studied in this work together with the results reported in literature: For ortho-acetoxybenzoic acid (aspirin) there are several values reported in literature. The temperature of fusion determined in this study (Tfus = 407.38 K) is 2.4 K larger than the average of 103 values reported in reference [26] and is 6.6 K, 5.3 K, and 1.8 K smaller than the values reported,

Acknowledgements

Thanks are due to Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal, and to Programa Ciência 2008 (PEst-C/QUI/UI0081/2013), for the financial support to CIQ-UP. A.R.R.P.A also thanks FCT, Operational Program and European Union for the award of the postdoctoral fellowship (SFRH/BPD/97046/2013).

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    Present address: Requimte, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre, 4169-007 Porto, Portugal.

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