Experimental and theoretical surface tension deviations in the binary systems propyl propanoate + o-, m- and p-xylene at 298.15 K

doi:10.1016/j.fluid.2004.12.009

Fluid Phase Equilibria

Volume 232, Issues 1–2, 25 May 2005, Pages 9-15

https://doi.org/10.1016/j.fluid.2004.12.009 Get rights and content

Abstract

This paper reports on the surface tension of the binary mixtures {propyl propanoate + o-xylene}, {propyl propanoate + m-xylene} and {propyl propanoate + p-xylene} at the temperature 298.15 K and atmospheric pressure, over the whole composition range. The surface tension deviations obtained were correlated with a Redlich–Kister type equation. These data were compared with five different theoretical approaches. Among them we apply the theories of Hildebrand and Scott for ideal solutions and their extension of Guggenheim's ideal solution equation, valid for systems containing molecules of significantly different size; the Brock and Bird theory, based only in the critical values of the pure compounds; the Sudgen's equation based in the parachor, which needs the knowledge of density for the whole composition in the mixture; and finally, the Prigogine's refined theory, which takes into account the critical values and the temperature dependence of surface tension. We will discuss results from those five theoretical models applied to the experimental data presented in this work, and also to other previously published data. Also, we will discuss the influence of the surface molar area parameter value on the models that need it.

Introduction

This work continues our studies on the excess thermodynamic properties of binary mixtures containing propyl propanoate and an aromatic hydrocarbon as components [1], [2], [3]. We present here the surface tension deviations for the binary systems propyl propanoate + o-xylene, +m-xylene, and +p-xylene at the temperature 298.15 K and atmospheric pressure, over the whole composition range. The mixtures presented are especially important because they are widely used as solvents for dyes. Also, xylenes are used as raw material in plastic industry to produce synthetic fibres and soft plastic for aircrafts and other vehicles. From a theoretical point of view, these compounds are very interesting to test the different theories published to predict the surface tension deviations in mixtures. In order to determine which of the most important theories on surface tension is able to account the position of the functional groups, we have obtained the surface tension deviation using different proposed models. Among them we apply the theories of Hildebrand and Scott [4] for ideal solutions (HSIS) and their extension of Guggenheim's ideal solution equation (HSEG), useful for systems containing molecules of significantly different size; the Brock and Bird theory (BBT), based only on the critical properties of the pure compounds [5]; the Sudgen's equation based on the parachor (SE) [6], and finally, Prigogine's refined theory (PRT), which takes into account the critical properties and the temperature dependence of surface tension [7].

Section snippets

Experimental

The chemicals employed were supplied by Fluka and Sigma-Aldrich. Their mass purities were propyl propanoate (Sigma-Aldrich, >99%), o-xylene (Fluka, ≥99%), m-xylene (Fluka, ≥99%) and p-xylene (Fluka, ≥99%). The substances were degassed by ultrasound and dried over molecular sieves (Sigma type 0.4 nm), and otherwise used as supplied.

The surface tension of the pure liquids and their corresponding mixtures was measured with a thermostated (within ±0.05 K) drop volume tensiometer LAUDA TVT1 with a

Results

The measured surface tension, σ, of the four pure liquids used at T = 298.15 K are listed in Table 1 together with literature values. We have included data from three different sources. The data for the xylenes from Refs. [9], [10], are exactly equal. These two reference books do not provide σ data for the propyl propanoate. The data obtained from Ref. [11] are around 1% larger for the four compounds than the data from Refs. [9], [10]. Within the experimental uncertainties, our data and the

Theoretical

In this section we will present five different theoretical models taken from literature. At present there are different theoretical or semi-empirical approximations to estimate the surface tension of a mixture from the corresponding values of the pure components [4], [5], [6], [7], [14], [15], [16], [17], [18]. To apply some of these models it is necessary to know other physical magnitudes of the liquid mixtures, as their density [6] or the critical parameters of the pure components [5], [7].

Discussion

As noted before, in Fig. 2, Fig. 3, Fig. 4 we plot the experimental surface tension deviations (δσ) measured, together with the results obtained for each of the five theoretical models presented in the previous section. We observe that none of the five equations reproduce the form of experimental curves. HSIS (continuous lines) and HSEG (dashed lines) equations present the best agreement in absolute value between experimental data and theoretical approximation but both are symmetrical, while

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Experimental and theoretical surface tension deviations in the binary systems propyl propanoate + o-, m- and p-xylene at 298.15 K

Abstract

Introduction

Section snippets

Experimental

Results

Theoretical

Discussion

Thermochim. Acta

J. Colloid Interf. Sci.

J. Colloid Interf. Sci.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Chem. Eng. Data

J. Therm. Anal. Calorim.

Solubility of Nonelectrolytes

AIChE J.

J. Chem. Soc.

J. Chim. Phys.

Adv. Mater.

Organic solvents, physical properties and methods of purification

Techniques of Chemistry, vol. II

J. Phys. Chem. Ref. Data