Study of intermolecular interactions through dielectric properties of the mixtures consisting of 1,4-butanediol, primary amyl alcohols and 1,4-dioxane at various temperatures

https://doi.org/10.1016/j.jct.2015.08.021Get rights and content

Highlights

  • Kirkwood factor values indicate parallel association for 1,4BD.

  • Heterogeneous interactions are significant in (1,4BD + AA or IAA) systems.

  • Positive ΔAE values were obtained over the whole composition range.

Abstract

This paper presents relative permittivities, excess permittivities, effective dipole moments, and excess Kirkwood correlation factors of binary mixtures of 1,4-butanediol with two primary pentanol isomers [1-pentanol (amyl alcohol) + 3-methyl-1-butanol (isoamyl alcohol)] from T = (298.15 to 318.15) K at p = 101.3 kPa over the entire composition range. Experimental permittivity values for polar–non-polar binary systems of (1,4-dioxane + amyl alcohol or isoamyl alcohol) were also obtained as a function of composition at the same range of temperatures. The experimental permittivity data were fitted using Redlich–Kister equation to evaluate the adjustable parameters and the standard errors. From the experimental data, the excess parameters were calculated. In this work, variations of effective dipole moment and correlation factor were investigated using Kirkwood−Frohlich equation. The experimental data of measurements were used in the analysis of the homo- and hetero interactions occurring in these binary solutions.

Introduction

Relative permittivity or static dielectric constant is a macroscopic and intrinsic property that provides important information about molecular associations and geometrical structure of molecules [1], [2], [3], [4], [5]. The permittivity data of binary systems (polar–polar and polar–non-polar) over a range of mole fractions and temperatures are crucial for understanding of the nature and strength of intermolecular interactions and the consequential structural rearrangement of molecules [6], [7], [8], [9]. Generally, type of solvent, concentration and temperature are very important factors that influence dielectric behavior of a liquid mixture [10].

Up to now, substantial dielectric studies have been carried out on many alcohol mixtures with various compositions and temperatures [11], [12], [13], [14]. Due to the presence of the –OH group in these molecules, the dielectric behavior of alcohols depend mainly on the dipole–dipole interactions, hydrogen bonding and local structure of the alcohol. However, in the case of diols, due to the presence of two –OH groups in the molecule, the dielectric properties and the dipole moments of the diols strongly influenced by the location of –OH groups (the separation of the two –OH groups along the carbon skeleton), molecular conformations and molecular flexibility. Moreover, formation of network structure in diols, due to the molecular association, is a well-known phenomenon [15]. In general, the permittivity of the diols depends on the distance between the hydroxyl groups along the chains of these molecules as well.

The diol used in this study was 1,4-butanediol (1,4BD) with two primary hydroxyl groups. In this molecule, the existence of two non-adjacent hydroxyl groups at positions 1 and 4 leads to the formation of a network structure [16]. Up to now, several authors have reported dielectric data and electric dipole moments for pure or various systems consisting of 1,4BD [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28].

The mono-alcohols studied are two primary pentanol isomers, namely 1-pentanol (amyl alcohol, AA) and 3-metyl-1-butanol (isoamyl alcohol, IAA). These isomeric pentanols were chosen in order to a comparative study of the influence of the chain branching on the dielectric properties of the alcohol/diol mixtures. Moreover, it is well known that heavy alcohols are useful chemical for the separation of diols from aqueous solutions. Thus, due to the structure characteristics of these isomers, they may be considered as good solvents for extraction of the diol. Consequently, the obtained dielectric results can be industrially and scientifically important.

Experimental permittivity and excess permittivity data for mixtures consisting of 1,4BD at different temperatures were reported in our previous publications [29], [30], [31]. As a continuation of the previous works, we present and discuss the results of a systematic study of the temperature and concentration dependence of the permittivity, excess permittivity, and effective dipole moment of the binary mixtures of 1,4BD with two primary pentanol isomers (amyl and isoamyl alcohol) over the temperature range of (298.15 to 318.15) K. In this work, a comparative dielectric study of intermolecular interactions was carried out in these binary systems over the entire composition range. In addition, in order to obtain additional information about the homo interaction between alcohol molecules, the dielectric measurements were obtained for the (amyl or amyl alcohols + 1,4DX) binary mixtures for the investigated temperature range.

Section snippets

Chemicals

1,4-butanediol (mass fraction purity > 0.98), amyl alcohol (mass fraction purity > 0.99), and isoamyl alcohol (mass fraction purity > 0.99) were obtained from Merck. 1,4-dioxane (mass fraction purity > 0.995) was supplied from AppliChem. HPLC grade cyclohexane (mass fraction purity > 0.999) was obtained from Merck and was used for the calibration of the dielectric cell. All chemicals were stored in dark bottles over molecular sieves (Merck 0.4 nm) to reduce water content. The chemical structures of the

Relative permittivity data

Relative permittivity and refractive index data were measured for the four binary systems of (1,4DX + AA), (1,4DX + IAA), (AA + 1,4BD), and (IAA + 1,4BD) over the complete mole fraction range (0x21).

In this research, the experimental permittivity data for the pure compounds were compared graphically with the literature data. Typically, figures 2(a–d) and 3(a–d) compare the experimental relative permittivity (εr) and refractive index (nD) data obtained for the pure liquids at different temperatures

Conclusions

Experimental relative values of permittivity for binary systems consisting of 1,4-butanediol with 1-pentanol (amyl alcohol) and 3-methyl-1-butanol (isoamyl alcohol)] were determined over the entire composition range at three different temperatures. Values of the dipole moment and Kirkwood correlation factor for the polar liquids were obtained in 1,4DX solutions and interpreted in terms of intermolecular interactions. For these mixtures, the permittivity results yield a Kirkwood factor, g > 1, and

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