Ultrasonic velocities, densities, and excess molar volumes of binary mixtures of N,N-dimethyl formamide with methyl acrylate, or ethyl acrylate, or butyl acrylate, or 2-ethyl hexyl acrylate at T = 308.15 K

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Abstract

Ultrasonic velocities, u, densities, ρ, of binary mixtures of N,N-dimethyl formamide (DMF) with methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), and 2-ethyl hexyl acrylate (EHA), including pure liquids, over the entire composition range have been measured at T = 308.15 K. Using the experimental results, the excess molar volume, VmE, partial molar volumes, V¯m,1, V¯m,2, and excess partial molar volumes, V¯m,1E, V¯m,2E have been calculated. Molecular interactions in the systems have been studied in the light of variation of excess values of calculated properties. The excess properties have been fitted to Redlich–Kister type polynomial and the corresponding standard deviations have been calculated. The positive values of VmE indicate the presence of dispersion forces between the DMF and acrylic ester molecules. Further theoretical values of sound velocity in the mixtures have been evaluated using various theories and have been compared with experimental sound velocities to verify the applicability of such theories to the systems studied. Theoretical ultrasonic velocity data have been used to study molecular interactions in the binary systems investigated.

Highlights

► Positive values of VmE, indicate dispersion forces between acrylic esters and DMF. ► VmE values compared with Redlich–Kister polynomial. ► Partial molar volumes data conclude that weak interactions exist in the systems. ► Measured velocity values compared with theoretical values obtained by polynomials.

Introduction

The study of properties of liquid mixtures and solutions finds direct applications in chemical and biochemical industry. The measurement of speed of sound in liquids enables determination of some useful acoustic and thermodynamic parameters that are found to be very sensitive to molecular interactions. Hence, such measurements are useful to study the strength of molecular interactions in liquid mixtures. Acrylic esters are important industrial chemicals and are widely used as precursors in the production of technically important special type polymers. Methyl acrylate is a contact allergen present in nail lacquer. It can also be used as a co-polymer in the process of polymerization of poly anionic cellulose (PAC) polymers, to reduce the glass transition temperature of the PAC polymers. Ethyl acrylate is a very important industrial chemical and is widely used commercially for the production of high polymeric and latex compounds. Butyl acrylate is a very useful feedstock for chemical synthesis, because it readily undergoes addition reaction with a wide variety of organic and inorganic compounds and N,N-dimethyl formamide is used as a solvent in peptide coupling for pharmaceuticals, in the development and production of pesticides, in the manufacture of adhesives, synthetic leathers, fibers, films, and surface coatings and other applications of pure solvents.

A survey of the literature indicates that Francesconi and Comelli [1], Gonzalez and Ortega [2], and Liau et al. [3] reported density and viscosity data for binary mixtures of esters with alkanols. Peralta et al. [4], [5], [6], [7] measured densities of ethyl acrylate, butyl acrylate, methyl methacrylate, and styrene with toluene/cyclohexane/benzene/1,4-dioxane at temperature 298.15 K. Recently some researchers have reported the ultrasonic, volumetric, and viscometric studies of esters with alcohols [8], [9], [10], [11], [12], [13]. The study of intermolecular interactions in (N,N-dimethyl formamide + acrylic esters) would be interesting owing to their industrial and pharmaceutical applications.

In the present paper, ultrasonic velocities, u and densities, ρ of binary mixtures of N,N-dimethyl formamide (DMF) with methyl acrylate (MA) or ethyl acrylate (EA) or butyl acrylate (BA) or 2-ethyl hexyl acrylate (EHA) besides those of pure liquids at temperature 308.15 K covering the entire composition range have been reported. The excess molar volume, VmE, partial molar volumes, V¯m,1, V¯m,2, and excess partial molar volumes, V¯m,1E, V¯m,2E have been calculated. The variations of excess properties with composition of the mixtures have been discussed in terms of molecular interactions in the mixtures. The experimental values of u and ρ of pure liquids at T = 308.15 K along with their literature [8], [14], [15], [16], [17] values are presented in table 1.

Section snippets

Experimental

The N,N-dimethyl formamide (mass fraction purity 0.99) and butyl acrylate (mass fraction purity 0.99) were obtained from LOBA Chemicals, and methyl acrylate (mass fraction purity 0.99), ethyl acrylate (mass fraction purity 0.99), and 2-ethyl hexyl acrylate (EHA) (mass fraction purity 0.99), obtained from KEMPHASOL Company, Bombay. All are Analytical Reagent grade (AR grade) used in the present investigation and are further purified by standard methods [18]. The solutions of binary mixtures of

Results and discussion

The excess molar volume, VmE was calculated using the relationVmE=x1M1+x2M2ρ-x1M1ρ1+x2M2ρ2,where M1, M2 and ρ1, ρ2 are the molar masses and densities of the pure components used in the present work; ρ is the density of the liquid mixture. The values of ρ, VmE and partial molar volumes V¯m,1, V¯m,2 are presented in table 2.

The values of VmE have been fitted to the Redlich–Kister type polynomial equation [23].YE=x1x2i=0nAi(x2-x1)i,where YE=VmE.

The values of Ai are the adjustable parameters of

Conclusions

The ultrasonic velocities and densities for (MA or EA or BA or EHA + DMF) binary mixtures have been measured and the values of VmE, V¯m,1, V¯m,2, and V¯m,1E, V¯m,2E have been calculated. The VmE values are positive in all the binary mixtures, indicating dispersion forces between the acrylate and DMF molecules and it follows the order (MA + DMF) > (EA + DMF) > (BA + DMF) > EHA > DMF. The observed higher partial molar volumes in the liquid mixture when compared to the respective molar volumes of pure components

Acknowledgements

Authors are grateful to University Grants Commission, New Delhi for providing infrastructure facilities under DRS Scheme to the Department of Physics, Acharya Nagarjuna University.

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