Intermolecular interactions in formamide + 2-alkoxyethanols: Viscometric study

doi:10.1016/j.tca.2012.03.001

Thermochimica Acta

Volume 537, 10 June 2012, Pages 57-64

https://doi.org/10.1016/j.tca.2012.03.001 Get rights and content

The viscosity (η) of formamide (FA) with 2-methoxyethanol (2-ME) and 2-ethoxyethanol (2-EE) has been measured at 303.15, 308.15, 313.15, 318.15 and 323.15 K over the entire composition range. From the experimental viscosity data, viscosity deviations (Δη) of binary mixtures were evaluated and fitted to the Redlich–Kister equation. The Δη values are positive over the entire range of composition for (formamide + 2-methoxyethanol) and (formamide + 2-ethoxyethanol) systems. The Grunberg–Nissan (d₁₂), Tamura–Kurata (T₁₂) and Hind (H₁₂) interaction parameters have been calculated. Furthermore, Gibbs free energy of activation (ΔG*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and excess Gibbs free energy of activation (ΔG*^E) of viscous flow have also been evaluated by using Eyring viscosity equation. The results are discussed in terms of molecular interactions due to physical, chemical and structural effects between the unlike molecules. It is observed that the strength of intermolecular interaction between FA and 2-alkoxyethanol molecules is in order: FA + 2-EE > FA + 2-ME.

Introduction

Viscometric properties of binary and multicomponent liquid mixtures are a powerful tool in understanding the nature and physico-chemical behaviour of molecular systems [1], [2], [3], [4], [5]. Viscosity is an important transport property for process design in petroleum, petrochemical, chemical and other chemical industries involving fluid transportation, mixing, agitation, filtration, heat exchange and concentration. The estimation of viscosity of a mixture is more difficult than that of the pure compound. The prediction of viscosity of liquid mixtures is a goal of long standing with both experimental and theoretical importance. Many industrial, chemical processes or laboratory works need experimental data of viscosity at any given temperature and composition for binary liquid mixtures. In continuation to our previous works [6], [7], [8], [9], [10], [11], [12] here we report the results of our studies on transport and thermodynamic properties of binary mixtures of formamide with 2-alkoxyethanols.

A detailed search in the literature [13], [14], [15], [16], [17], [18], [19], [20], [21] shows that some investigations have been carried out on acoustic and thermodynamic properties of amide–alcohol mixtures. Formamide is the simplest molecules containing a peptide linkage ( single bond NHCO) and a study of their hydrogen bonding yields into the nature of protein structure [1]. Formamide molecules are highly polar (μ = 3.37 D at 298.15 K) [22] and are strongly self-associated through extensive three-dimensional network of hydrogen bonds, through its three hydrogen bond donors (3 H-atoms) and three acceptors (two lone pairs of electrons at oxygen and one at nitrogen atom) [23], [24]. Alkoxyethanols are polar (μ_ME = 2.23 D and μ_EE = 2.31 D), non-ionic amphiphile molecules, very effective surfactants with a large number of applications [25], [26], [27], [28]. On the other hand, the investigation of mixtures involving alkoxyethanols makes possible the study of self-association via inter- and intra molecular hydrogen bonds related to the presence of the single bond O and OH groups in the same molecules [29], [30], [31]. The presence of etherial oxygen enhances the ability of OH group of the same molecule to form hydrogen bonds with other unlike molecules.

The binary systems of formamide with 2-methoxyethanol and 2-ethoxyethanol are of considerable interest for investigating the intra- and intermolecular behaviour of amido-alcoholic solvent systems. To the best of our knowledge, there has been no temperature dependent study on these systems from the view point of their viscometric behaviour. This fact allows us to plan some extensive studies in this research field in order to investigate the closest interactions between the unlike molecules by examining the transport and thermodynamic parameters. We have reported a detailed investigation on the density (ρ) and viscosity (η) of binary mixtures of formamide with 2-ME and 2-EE at 303.15, 308.15, 313.15, 318.15 and 323.15 K covering the entire miscibility range (0 < x < 1). From the experimental values of viscosity (η), the deviations in viscosity (Δη) have been evaluated. The Grunberg–Nissan (d₁₂), Tamura–Kurata (T₁₂) and Hind (H₁₂) interaction parameters have been calculated. Furthermore, Gibbs free energy of activation (ΔG*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and excess Gibbs free energy of activation (ΔG*^E) have also been evaluated from the experimental viscosity data.

Section snippets

Experimental

The chemicals used were of analytical grade, formamide (Merck, mass fraction purity >0.990), 2-methoxyethanol and 2-ethoxyethanol (S. D. Fine Chemicals Ltd., mass fraction purity >0.995) and were used after single distillation. Mixtures were stored in glass stoppered flasks to avoid contamination and evaporation. All mixtures were prepared by mass using Sartorius electronic balance, model CPA225D, with a precision of ±0.01 mg. Density measurements were made using a single-capillary pycnometer

Results and discussion

The experimental values of density and viscosity for pure FA, 2-ME and 2-EE at 303.15, 308.15, 313.15, 318.15 and 323.15 K, compared with the available literature values, are recorded in Table 1. The experimentally measured values of viscosity (η) with the viscosity deviation (Δη) for FA + 2-ME and FA + 2-EE at various temperatures are listed in Table 2, Table 3, respectively.

The deviations in viscosity have been evaluated using the relation [38]: $Δ η = η_{(m i x)} - \sum_{i} x_{i} \cdot η_{(i)}$ where x_i, η_(i) and η_(mix) are mole

Conclusions

In the present investigation, the density and viscosity of the binary mixtures of formamide with 2-alkoxyethanols have been experimentally determined at T = 303.15, 308.15, 313.15, 318.15 and 323.15 K. The observed transport and thermodynamic parameters are positive over the entire composition range, which revealed the behaviour of hetero-molecular interactions at the molecular level. The results were analyzed in terms of the molecular characteristics of the interacting molecules and found to

Acknowledgement

The authors are thankful to the University Grant Commission, New Delhi, for providing financial support under a Major Research Project [F. No. 33-34/2007 (SR)].

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Intermolecular interactions in formamide + 2-alkoxyethanols: Viscometric study

Introduction

Section snippets

Experimental

Results and discussion

Conclusions

Acknowledgement

J. Mol. Liquids

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Mol. Liquids

Ultrasonics

Fluid Phase Equilib.

J. Mol. Liquids

J. Mol. Liquids

J. Mol. Liquids

J. Mol. Spectrosc.

J. Chem. Thermodyn.

J. Mol. Liquids

J. Chem. Thermodyn.

J. Mol. Liquids

Fluid Phase Equilib.

J. Chem. Thermodyn.

The viscosity of liquid mixtures

AIChE J.

Structure viscosity of liquid-camphor and pyrene mixtures

Trans. Faraday Soc.

Densities viscosities and refractive indices for binary and ternary mixtures of N,N-dimethylacetamide (1) + 2-methylbutan-2-ol (2) + ethyl acetate (3) at 298.15 K for the liquid region and at ambient pressure

J. Chem. Eng. Data

Integral isobaric heats of vaporization of methanol + 1,2-dichloroethane + 1,1,1-trichloroethane mixtures

Phys. Chem. Liquids

Study of molecular properties using acoustic non-linearity parameter in the ternary liquid mixtures at different temperatures

Phys. Chem. Liquids

Estimation of acoustic nonlinearity parameter and molecular characteristics of ternary liquid mixtures

Can. J. Phys.

Ultrasonic and IR investigations of N–H bond complexes

Phys. Chem. Liquids

Ultrasonic study on binary mixture containing dimethylformamide and methanol over the entire miscibility range (0 < x < 1) at temperatures 303–323 K

Fluid Phase Equilib.

Ultrasonic and viscometric studies of molecular interactions in binary mixtures of formamide with ethanol 1-propanol, 1,2-ethanediol and 1,2-propanediol at different temperatures

Indian J. Phys. B

Volumetric and viscometric studies on N,N-dimethylacetamide + 1-hexanol/1-heptanol binary liquid mixtures at different temperatures

Indian J. Pure Appl. Phys.

Density, refractive index, and speed of sound in binary mixtures of 2-ethoxyethanol with dimethyl sulfoxide, N,N′-dimethylformamide, N,N′-dimethylacetamide at different temperatures

J. Chem. Eng. Data

N,N-dimethylformamide + 2-methoxyethanol binary mixtures Viscosity and activation energy of viscous flow at various temperatures

Bull. Chem. Soc. Jpn.

N,N-dimethylformamide-2-methoxyethanol solvent system. Densities and excess molar volumes at various temperatures

J. Chem. Soc. Faraday Trans.