Thermophysical and optical studies of molecular interactions in binary mixtures of diethyl carbonate with aromatic compounds at temperatures from 298.15 to 323.15 K

doi:10.1016/j.jct.2016.08.001

The Journal of Chemical Thermodynamics

Volume 103, December 2016, Pages 17-29

https://doi.org/10.1016/j.jct.2016.08.001 Get rights and content

Highlights

•
Density, speeds of sound and refractive index has been measured of DEC with aromatic hydrocarbons between 298.15 and 323.15 K.
•
$V_{m}^{E}$ and $κ_{s}^{E}$ are negative in the whole composition range may be attributed to strong ion–ion/dipole-dipole interaction.
•
The effect of temperature and concentration on density, speed of sound and refractive index have been discussed.

Abstract

In the present investigation, experimental densities, speeds of sound and refractive indices of binary mixtures of diethyl carbonate (DEC) with three aromatic compounds of varying nature (Aniline, Benzonitrile and Benzaldehyde) have been measured over the entire composition range at different temperatures from 298.15 K to 323.15 K employing a vibrating-tube densimeter DSA 5000M at ambient pressure 0.1 MPa. Excess molar volume, excess isentropic compressibility, excess speeds of sound and deviations in molar refraction were calculated from the density and speed of sound results. Excess properties were correlated with the Redlich–Kister polynomial equation. Values of partial excess volumes at infinite dilution for these three binary systems at different temperatures were calculated from the adjustable parameters of the Redlich–Kister smoothing equation. The excess isobaric coefficients of thermal expansion of three binary mixtures have been estimated from temperature dependence of densities. It is seen that all excess properties are negative over the entire range of composition and temperature. Strong molecular interactions are seen to exist between diethyl carbonate and aromatic compounds. The system (DEC + aniline) exhibits the maximum negative deviation from ideality among the three systems, resulting from multiple factors such as the partial interstitial accommodation effect, steric hindrance, the size of molecule and the instantaneous dipole induced dipole interactions.

Graphical abstract

Introduction

Over the past several decades, Ultrasonic investigations have gained the status of an absolutely essential and increasingly significant parameter for the investigations related to structure of molecules and properties of matter. The utilization of speed of sound is one of the most noteworthy and natural methodologies for the investigation of molecular collaborations in fluids. Speed of sound plays a vital role in the examination of intermolecular interactions. It is a well-known fact that the structural behaviours are impacted by the shape of the molecules and by their mutual interactions.

For the design of separation equipment and to test theories of solutions, there is a constant need for thermodynamic excess property data. In addition, excess properties provide information about the molecular interactions and macroscopic behaviour of fluid mixtures [1], and can be used to test and to improve thermodynamic models for calculating and predicting fluid phase equilibria.

The study of intermolecular interaction of DEC with aromatic compounds (Aniline, Benzonitrile and Benzaldehyde) would be of singular interest owing to its industrial applications. Literature survey reveals lack of temperature dependent study of these systems from the point of view of their density, speed of sound and optical behaviour. DEC has been chosen because of its multifarious applications such as its role as an ethylating and carbonylating reagents in organic synthesis, nitro-cotton, cellulose ether, synthetic resin and natural resin in the textile, printing and dyeing industry and preparation of the electrolyte in the capacitor and lithium battery, fuel, lube additive, paint and plastic industry. It is a basic ingredient in the pharmaceutical industry and has been used to synthesize intermediate phenobarbital etc. Aniline exists in associated form whereas benzonitrile has a non-associated structure in the liquid state. Aniline molecules are polar protic [2] and self-associated in the pure state through hydrogen bonding of their amino groups [3]. Aniline has been used as parent substance in the manufacture of several chemical products and intermediates, in the production of isocyanides, rubber chemicals, dyes and pigments, hydroquinone, drugs and agriculture. It is also used as a solvent and has been used as an antiknock compound for gasoline [4]. Benzaldehyde molecules are polar aprotic [5], is the simplest representative of the aromatic aldehydes, occurring naturally as the glycoside amygdalin and has been used in the manufacture of dyes, cinnamic acid, to some extent in perfumes and flavouring agents and used as a precursor to other organic compounds, ranging from pharmaceuticals to plastic additives. Benzonitrile molecules are polar aprotic, used as a solvent and intermediate in industries making drugs, perfumes, dyes, rubber, textiles, resins, and specialty lacquers.

Section snippets

Chemicals

Diethyl carbonate (DEC), Aniline, Benzonitrile and Benzaldehyde used in the present study have been procured from Sigma Aldrich, with mass purity >0.99 and have been purified by the methods described in literature [6], [7].The water content of all samples was less than 0.006%. All provenance and mass fraction purity of the used materials are listed in Table 1. The density, speed of sound and refractive index measured at various temperatures were compared with values available in the literature

Excess properties

For this binary system, the excess molar volume $V_{m}^{E}$ was calculated using the experimental mixture and the pure components densities as described by equation $V_{m}^{E} = \sum_{i = 1}^{2} x_{i} M_{i} (ρ - ρ_{i}^{- 1})$ where $ρ$ is density of mixtures and $M_{i}, x_{i}$ and $ρ_{i}$ are the molar mass, mole fraction and density of the pure component $i$ , respectively.

The excess isentropic compressibility, $κ_{s}^{E} = κ_{s} - κ_{s}^{id},$ was calculated using the rigorous thermodynamic ideal-mixing rule for isentropic compressibility $κ_{s}^{id}$ . The isentropic compressibility of

Results and discussion

The excess molar volume ( $V_{m}^{E}$ ) values are seen to be negative over the entire mole fraction range with the values being highest (negative) in the equimolar region. A close perusal of Fig. 1 shows that the excess molar volume values show an increase, more negative, with increase in temperature from 298.15 K to 323.15 K. Taking into account the fact that aniline is a primary amine, self-associated through H-bonds, the negative values may be attributed to several factors. A prime reason may be

Molar refraction

The molar refractivity reflects arrangements of the electron shells of ions in molecules and yields information about the electronic polarization of ions. The molar refractivity reflects the changes in the properties due to polarization or to deformation of the electron shells of the ions under the influence of the electric fields of neighbouring ions [43]. Refractive indices have been used for the calculation of molar refraction (R_m) using Lorentz-Lorenz [44], [45], [46] equation $R_{m} = \frac{[n_{D}^{2} - 1]}{[n_{D}^{2} -}$

Conclusion

In the present investigation, density, speed of sound and refractive index have been measured for the binary mixtures of (DEC + aniline)/benzonitrile/benzaldehyde at atmospheric pressure and intervals of 5 K from T = (298.15–323.15) K over the entire range of compositions. Excess molar volume, $V_{m}^{E}$ , excess isentropic compressibility, $κ_{s}^{E},$ and molar refraction deviation on volume fraction basis, $Δ R_{m}$ ,were obtained from experimentally determined values of the aforementioned parameters. The values of $V_{m}^{E}$

References (52)

P. Vasundhara et al.
J. Mol. Liq.
(2015)
M. Srilakshmi et al.
J. Mol. Liq.
(2015)
T. Srinivasa Krishna et al.
J. Mol. Liq.
(2015)
M.A. Rivas et al.
J. Chem. Thermodyn.
(2004)
Laura. Mosteiro et al.
J. Chem. Thermodyn.
(2009)
E.R. Lopez et al.
J. Chem. Thermodyn.
(2000)
Sanjeevan J. Kharat et al.
J. Mol. Liq.
(2007)
V.K. Sharma et al.
J. Mol. Liq.
(2013)
Toshiharu Takagi et al.
J. Chem. Eng. Data
(1988)
Naved I. Malek et al.
Thermochim. Acta
(2012)

G.C. Benson et al.

J. Chem. Thermodyn.

(1979)

Ranjan Dey et al.

J. Mol. Liq.

(2009)

Fuchun Chen et al.

J. Mol. Liq.

(2015)

H. Wang et al.

J. Chem. Thermodyn.

(2004)

M.P. Patel et al.

Biomaterials

(1992)

B. Orge et al.

J. Chem. Thermodyn.

(2000)

R. Munoz et al.

Fluid Phase Equilib.

(2000)

Santosh Kumar et al.

J. Mol. Liq.

(2010)

R.C. Reid et al.

The Properties of Gases and Liquids

(1998)

J.A. Dean

Lange’s Handbook of Chemistry

(1956)

J. Feeney et al.

J. Chem. Soc.

(1962)

I.M. El-Anwar et al.

J. Mater. Sci. Technol.

(1995)

J.A. Riddick et al.

Organic Solvents: Physical Properties and Methods of Purification

(1986)

A.I. Vogel

Text Book of Practical Organic Chemistry

(1989)

L. Mosterio et al.

J. Chem. Thermodyn.

(2001)

M.V. Ratnam et al.

J. Mol. Liq.

(2013)

Cited by (17)

Experimental, theoretical and spectroscopic analysis of molecular interactions in binary liquid mixtures comprising ionic liquid and alkyl cellosolves
2024, Journal of the Taiwan Institute of Chemical Engineers
To design any green chemical process and/or reaction involving ionic liquids (ILs) on an industrial scale, it is necessary to know thermophysical properties of the pure ILs and its solutions with different solvents in wide temperature and composition range.
In this study, thermodynamic functions such as density, ρ, viscosity, η and refractive index, n_D have been used to clarify the changes in the solution structure and interaction of 1-butyl-3-methylimidazolium bromide/2-alkoxyethanols system in response to changes in temperature and composition. From the experimental results, excess thermodynamic parameters have been calculated. The obtained data have been fitted to Redlich-Kister equation to obtain the binary coefficients and standard deviations between experimental and best-fit values. The Graph and Prigogine-Flory-Patterson theories have been employed to correlate experimental $V_{m}^{E}$ values. Quantum chemical calculations of molecular cluster of IL and 2-alkoxyethanols were performed in support of predicting structures by Graph theory. Furthermore, Fourier-transform infrared and Raman spectrum of investigated solutions were finally compared and discussed by the viewpoint of molecular interactions.
The formation of extensive hydrogen bonding between [BMIM]Br and 2-alkoxyethanols was considered as the main driving force for non-ideal behaviour of these binaries.
Electrical conductivity and refractive index of binary ionic liquid mixtures with diethyl carbonate, dimethyl carbonate and propylene carbonate
2023, Journal of Molecular Liquids
Four imidazolium-type ionic liquids (ILs) [Emim][NTf₂], [Emmim][NTf₂], [Bmim][NTf₂] and [Bmmim][NTf₂] have been synthesized and used to prepare binary mixtures with organic solvents dimethyl carbonate (DMC), Diethyl carbonate (DEC), and propylene carbonate (PC), respectively. The electrical conductivity and refractive index of the mixtures were measured and discussed from 293.15 to 323.15 K. The dependence of electrical conductivities of the binary mixtures on the concentration of mole fraction and temperature were fitted from the empirical Casteel-Amis (CA) equation and Vogel-Fulcher-Tamman (VFT) equation, respectively. The maximal conductivities were discussed from the fitted values for the ILs with different solvents. The dependence of refractive indexes of the binary mixtures on the concentration of mole fraction and temperature were also fitted from the Redlich-Kister polynomial equation and linear equation. Moreover, the influences of introducing methylene and methyl into the cation of ILs on their properties are discussed.
Insight into intermolecular interactions in benzonitrile + methyl acrylate/ethyl acrylate/n-butyl acrylate/t-butyl acrylate binary mixtures at temperatures from 293.15 to 318.15 K: Ultrasonic and viscometric study
2021, Journal of Molecular Liquids
Citation Excerpt :
The temperature of the test liquids during the measurements was maintained to an uncertainty of ±0.01 K in an electronically controlled thermostatic water bath (JULABO, Model: ME-31A, Germany). The reliability of experimental measurements of u and η was ascertained by comparing the experimental data of pure liquids with the corresponding literature [28–44] values (Table 2) and the agreement between the values obtained in the present work and those reported in the literature is found satisfactory, in general. The measured values ultrasonic speeds, u and viscosities, η of binary mixtures of BN with MA, EA, n-BA and t-BA as functions of mole fraction, x1 of BN and temperature are listed in Tables 3 and 4, respectively.
The ultrasonic speeds, u and viscosities, η of binary mixtures of benzonitrile with alkyl acrylate (methyl acrylate, ethyl acrylate, n-butyl acrylate and t-butyl acrylate) over the entire composition range, including the pure liquids, were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and at pressure, p = 101 kPa. From the experimental data, the excess isentropic compression, κ_s^E, excess ultrasonic speed, u^E, excess molar isentropic compression, K_{s, m}^E and deviations in viscosity, Δη have been calculated. The excess properties were correlated by the Redlich-Kister polynomial equation. The partial molar isentropic compressions and excess partial molar isentropic compressions over the whole composition range; and partial molar isentropic compressions and excess partial molar isentropic compressions of the components at infinite dilution have also been calculated. The variations of these parameters with composition and temperature have been discussed in terms of intermolecular interaction prevailing in these mixtures. Further, the η data of these mixtures were theoretically correlated with various empirical and semi-empirical models and the results were compared with the experimental data.
Thermodynamic and theoretical investigations on [Emim][Bf<inf>4</inf>]/[Bmim][Bf<inf>4</inf>] and aniline binary mixtures
2019, Journal of Chemical Thermodynamics
Viscosity and refractive index values are measured for various binary compositions of 1-ethyl-3-methylimidazolium tetrafluoroborate/1-butyl-3-methylimidazolium tetrafluoroborate and aniline at temperatures from T = (293.15 to 323.15) K under atmospheric pressure. The experimental data is used to calculate molar Gibbs free energy of activation, enthalpy, entropy and also the excess values of viscosity, refractive index, molar Gibbs free energy of activation. Various theoretical models are used to estimate the refractive index values. Redlich-Kister equation is used to estimate the deviations between the calculated and experimental excess values. The variations in the calculated parameters are analysed to understand the nature of molecular interactions between the chemical species. The assumptions on the behaviour of molecular interactions from the analysis of excess parameters are supported by the experimental and computational FT-IR studies.
Densities, speeds of sound and excess properties of (benzonitrile + methyl methacrylate, or + ethyl methacrylate, or + n-butyl methacrylate) binary mixtures at temperatures from 293.15 K to 318.15 K
2019, Journal of Chemical Thermodynamics
Citation Excerpt :
The comparison of experimental values of density and speeds of sound for pure components with literature values at investigated temperatures is provided in Table 2 [15–34].
Experimental measurements of densities and ultrasonic speeds for the binary mixtures of benzonitrile with methyl/ethyl/n-butyl methacrylates over the entire composition range were carried out in the temperature range 293.15 K–318.15 K and atmospheric pressure of 0.1 MPa. Using the experimental data, the excess molar volume, excess ultrasonic speed, excess isentropic compressibility, and excess molar isentropic compressibility have been calculated and correlated by Redlich-Kister equation. The partial molar and excess partial counterparts of molar volumes and molar compressibilities over the whole composition range; and at infinite dilution have also been calculated. The dependence of these parameters on composition and temperature has been interpreted in terms of intermolecular interactions prevailing in these mixtures. The order of interactions suggested by the excess functions is found to be MMA > EMA > BMA. The major cause of the order is the steric hindrance caused by alkyl group. The results showed the effect of varying chain length on excess functions and interactions of the system.
A novel and effective approach for viscosity prediction of binary and multicomponent liquid mixtures
2018, Journal of Molecular Liquids
Citation Excerpt :
Literature survey reveals that amongst all the excess properties investigated, the most relevant and hence extensively investigated is excess volume and its molar counterpart [5–7]. The magnitude and sign of excess volume gives crucial information related to the type, nature and extent of the intermolecular interactions prevalent in the system under investigation [5]. An overview of the work carried out in the past few years [8–15] shows that a fairly large number of researchers from across the globe have reported excess molar volume to explain the experimental behaviour of the mixtures under consideration.
For the first time, to the best of our knowledge, a volume fraction based model has been developed for prediction of viscosity. The proposed model has been tested on 200 binary, 20 ternary and 5 quaternary liquid mixtures over a wide range of temperature. The results have been compared with other well-known predictive equations taking average absolute percentage deviation (AAPD) as the criterion for predictive capability. Grand AAPDs show that the proposed model is outperforming all the well-known approaches in terms of predictive capability.

View all citing articles on Scopus

View full text

Thermophysical and optical studies of molecular interactions in binary mixtures of diethyl carbonate with aromatic compounds at temperatures from 298.15 to 323.15 K

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals

Excess properties

Results and discussion

Molar refraction

Conclusion

J. Mol. Liq.

J. Mol. Liq.

J. Mol. Liq.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Mol. Liq.

J. Mol. Liq.

J. Chem. Eng. Data

Thermochim. Acta

J. Chem. Thermodyn.

J. Mol. Liq.

J. Mol. Liq.

J. Chem. Thermodyn.

Biomaterials

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Mol. Liq.

The Properties of Gases and Liquids

Lange’s Handbook of Chemistry

J. Chem. Soc.

J. Mater. Sci. Technol.

Organic Solvents: Physical Properties and Methods of Purification

Text Book of Practical Organic Chemistry

J. Chem. Thermodyn.

J. Mol. Liq.