Elsevier

Thermochimica Acta

Volume 540, 20 July 2012, Pages 61-68
Thermochimica Acta

Excess molar volumes of (1-chlorobutane + heptane + 2-butanone or 2-pentanone) at (288.15, 303.15 and 313.15) K. Measurements and correlations

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Abstract

Experimental densities for the ternary mixtures x1 1-chlorobutane + x2 n-heptane + (1  x1  x2)2-butanone or 2-pentanone and five corresponding binary systems have been measured at T = (288.15, 303.15 and 313.15) K and atmospheric pressure, using a DMA 5000 Anton Paar densimeter. Excess molar volumes have been calculated using the measured experimental densities of the pure liquids and mixtures. The VE results were correlated and fitted by the Redlich–Kister equation for binary mixtures and by the Nagata and Tamura equation for ternary mixtures, as a function of mole fraction. Several predictive empirical relations were applied to predict the excess molar volumes of ternary mixtures from the binary mixing data. The excess molar volumes for the two ternaries are positive over the entire range of composition and at temperature between 288.15 K and 313.15 K.

Highlights

► Many engineering application often require data on the excess volumes VE of fluids. ► VE provide information about molecular interactions in ours mixtures. ► Geometrical solution models are used to predict the VE of ours ternaries. ► A good agreement between ours experimental results and predicted values.

Introduction

The thermodynamics of ternary mixtures of non-electrolytes has not received as much attention as the thermodynamics of binary mixtures. It is therefore interesting to estimate excess properties for systems with more than two components. As the number of components in the mixture increases, the determination of thermodynamic properties becomes more arduous. Therefore, the applicability of predictive methods is of great interest for estimating ternary properties from the experimental data of the binaries involved. In this work we present at T = (288.15, 303.15 and 313.15) K the excess molar volumes, VE, of the ternary systems x1 1-chlorobutane + x2 n-heptane + (1  x1  x2)2-butanone or 2-pentanone and the binary systems x 1-chlorobutane + (1  x) (n-heptane, 2-butanone or 2-pentanone) and x n-heptane + (1  x) 2-butanone or 2-pentanone. The binary experimental data were fitted to Redlich–Kister equation [1]. The Nagata and Tamura equation [2] has been used in order to correlate adequately the experimental values of VE of ternary mixtures. The experimental values were also used to test different symmetric [1], [3], [4] and asymmetric [5], [6], [7] empirical expressions. Asymmetry is usually understood to be caused by the strongly polar or associative behavior of any of the compounds in the mixture. In these cases, different geometric criteria are applied to match each point of ternary composition with the contributing binary compositions.

A survey of the literature indicates that volumetric properties of binary mixtures of 1-chlorobutane + 2-butanone or 2-pentanone have been studied by other authors [8], [9] at (298.15, 308.15) K. Also excess molar volumes were performed for n-heptane + 1-chlorobutane [10] at (283.15, 298.15, 313.15) K and for n-heptane + 2-butanone [11] at 293.15 K. For the other systems presented in this work, the density data are not available in the literature.

Section snippets

Experimental

The liquids 1-chlorobutane, n-heptane, 2-pentanone and 2-butanone were obtained from Fluka AG. The purity of substances was not less than 99% in mole fraction and was checked by comparing the measured densities with those reported in the literature [12], [13], [14], [15], [16], [17], [18] and also by chromatographic analysis. The values are listed in Table 1.

Densities of pure components and mixtures were measured at T = (288.15, 303.15 and 313.15) K with Anton Paar vibrating-tube densimeter DMA

Results and discussion

The excess molar volumes VE for the five binary systems and the corresponding ternary system were evaluated using the following equation:VE=Vi=1nxiMiρiV=i=1nxiMiρwhere xi, Mi and ρi are the mole fraction, molar mass and the density of component i respectively, ρ the measured density of the solution.

The uncertainty in the VE calculation is less than ±10−8 m3 mol−1. VE for the binary systems were fitted by the least squares method to the Redlich–Kister [1] equation:VE=x(1x)i=1nAi(2x1)i1

References (18)

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    The density measurements along with calculated excess molar volumes for the four systems are shown in the Supporting information. With respect to the comparison at atmospheric pressure of our results with early published ones [12–16], the agreement is reasonable with an average absolute deviation in excess volume of 0.013 cm3 mol−1. Only for the system n-heptane + 2-chloro-2-methylpropane at T = 298.15 K [13] the differences are more marked with an average absolute deviation in VE values of 0.021 cm3 mol−1.

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    Thereby we have made a comparison with the values generated by our correlation (equations (5)–(7) and table 3) at exactly the same experimental p, T sets given for several references, with the requirement that the p, T sets are in our experimental ranges for which our correlation has been built, in order to avoid any extrapolation. For pure components, table 4 presents a summary of literature data for 1-heptanol at atmospheric pressure [13–24] and at high pressure [12,25–30], while table 5 presents the same for heptane, [13,31–56] at atmospheric pressure and [57–73] at high pressure. In tables 4 and 5, N stands for the number of data points of each reference.

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