Elsevier

Fluid Phase Equilibria

Volume 385, 15 January 2015, Pages 105-119
Fluid Phase Equilibria

Speeds of sound, isentropic compressibilities and refractive indices for some binary mixtures of nitromethane with chloroalkane at temperatures from 298.15 to 318.15 K. Comparison with theories

https://doi.org/10.1016/j.fluid.2014.10.004Get rights and content

Abstract

The experimental data of speed of sound and refractive index for eight binary liquid mixtures of nitromethane with: 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1-chlorobutane and 1-chloropentane, have been measured at temperatures in the range of 298.15–318.15 K and atmospheric pressure. From the experimental data of densities and speeds of sound, the isentropic compressibilities and the excess isentropic compressibilities were calculated and from the experimental data of refractive indices, the deviation in refractive indices and the molar refractions have been computed. These excess properties of the binary mixtures were correlated by the Redlich–Kister type polynomials using a robust regression along a gnostic influence function. Speeds of sound and isentropic compressibilities have been compared with calculated values from Jacobson free length theory (FLT), Nomoto’s relation (NR), Zhang Junjie’s relation (JR), Van Deal’s ideal mixing relation (IMR) and Impedance dependence relation. The ability of different theoretical (n, ρ) mixing rules (Lorentz–Lorenz, Gladstone–Dale, Arago–Biot, Edwards and Eykman) to predict the refractive indices was evaluated. The experimental and calculated results are discussed in terms of molecular interactions and structural effects between components of mixtures.

Introduction

Nitroalkanes and chloroalkanes represent a class of technically important compounds used in industry as intermediates for organic synthesis or as final products.

Nitromethane is a polar liquid used as a solvent in a variety of industrial applications, such as in extractions, as a reaction medium, and as a cleaning solvent. It is principally used as stabilizer for chlorinated solvents, with high importance in degreasing, dry cleaning and semiconductor processing. The chloroalkanes have a practical importance as solvents, foaming agents, refrigeration fluids and air conditioning systems; they are also of great importance because of their impact in the environment cleaning.

The mixtures of nitroalkane + chloroalkane are studied experimentally to obtain the necessary data for the separation processes design in chemical plants. Simultaneously, these experimental data are very useful for developing the new thermodynamic properties predictive methods and for verifying the existing theories of liquids.

The present work is a continuation of our systematic study on the thermodynamic and thermophysical properties for nitroalkanes with chloroalkanes mixtures [1], [2], [3], [4], [5].

In our paper we present the excess data of speed of sound, isentropic compressibility and refractive index for eight binary liquid mixtures of nitromethane with: 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloromethane, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1-chlorobutane and 1-chloropentane, at three temperatures (298.15, 308.15, and 318.15) K and atmospheric pressure, over the whole range of composition.

To the best of our knowledge, for these binary systems of nitromethane with chloroalkanes, such data (at the working temperatures and compositions) have not been reported in the literature [6]. Data for refractive indices, only at T = 298.15 K, for nitromethane + 1,2-dichloroethane, +1,3-dichloropropane, +1,4-dichlorobutane were reported recently [7].

Section snippets

Speed of sound

The densities and speeds of sound data for the pure liquids and the binary mixtures were simultaneously measured using a digital vibrating-tube densimeter and speed of sound analyzer (Anton Paar DSA 5000 M) with an accuracy of ±0.001 K for temperature, ±0.05 kg m−3 for density and ±0.01 m s−1 for speed of sound, respectively.

The DSA 5000 M automatically corrects the influence of viscosity on the measured density. The apparatus was calibrated by measuring the density and sound velocity of dry air and

Speeds of sound and isentropic compressibility deviations

The deviations of the speed of sound (u) from their values in an ideal mixture (uid) were calculated from the equation:Δu=uuidwhere uid was calculated using the equation:uid=(Vmid)1/2(kS,midΣiϕiρi*)1/2where Vmid is the ideal molar volume, ρi* is the density of the pure liquid component i

and ϕi is the volume fractions of the pure component i, defined by the equation:

φi=ωiρijρi, in which ωi=xiMixiMi

kS,mid is the ideal mixing isentropic compressibility, defined by the approach developed by

Theoretical

In this paper, the speeds of sound in the binary liquid mixtures were also calculated using well known empirical and semi-empirical theories: Jacobson free length theory (FLT) [38], [39], Nomoto relation (NR) [40], Junjie relation (JR) [41], Van Deal ideal mixing relation (IMR) [42], [43] and Impedance dependence relation (IDR) [44].

The above mentioned theories provide the speeds of sound in the n-component mixture by the following equations:

Results and discussions

The results of ultrasonic speed, u, and the isentropic compressibility, kS, for all the studied binary mixtures, at T = (298.15, 308.15, and 318.15) K and atmospheric pressure, are presented in Table 3. The densities ρ required to calculate isentropic compressibilities kS (kS = 1/(u2ρ)) were taken from our previous paper [5].

The calculated speeds of sound, u, of the binary mixtures with the above presented theories are shown comparatively with the experimental values in Table 4.

The data of the

Conclusion

New experimental speed of sound and refractive index values, at T = (298.15, 308.15, and 318.15) K and atmospheric pressure, for eight binary mixtures of nitromethane with 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, chloroform, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1-chlorobutane, and 1-chloropentane were measured.

The excess speed of sound values are negative for all studied systems, and the excess isentropic compressibility values are positive for almost all the

Acknowledgements

This contribution was carried out within the research programme “Chemical Thermodynamics and Kinetics’’ of the “Ilie Murgulescu’’ Institute of Physical Chemistry, financed by the Romanian Academy. Support of the EU (ERDF) and Romanian Government, for the acquisition of the research infrastructure under Project INFRANANOCHEM–Nr. 19/01.03.2009, is also gratefully acknowledged.

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