Densities and volumetric properties of (acetonitrile + an amide) binary mixtures at temperatures between 293.15 K and 318.15 K

doi:10.1016/j.jct.2006.01.015

The Journal of Chemical Thermodynamics

Volume 38, Issue 11, November 2006, Pages 1362-1370

https://doi.org/10.1016/j.jct.2006.01.015 Get rights and content

Abstract

The densities of binary mixtures of acetonitrile (ACN) with formamide (FA), N,N-dimethylformamide (DMF), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA), including those of pure liquids, over the entire composition range were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and atmospheric pressure. From the experimental data, the excess molar volume, $V_{m}^{E}$ , and partial molar volumes, ${\bar{V}}_{m, 1}$ and ${\bar{V}}_{m, 2}$ , were calculated over whole composition range. The variation of these parameters with composition and temperature of the mixtures has been discussed in terms of molecular interaction in these mixtures. The $V_{m}^{E}$ values were found negative for all the mixtures and at each temperature studied, indicating the presence of specific interactions between ACN and amide molecules. The extent of negative deviations in $V_{m}^{E}$ values follows the order: FA > NMA > DMA > DMF. It is observed that the $V_{m}^{E}$ values depend upon the positions of methyl groups in these amide molecules.

Introduction

The multi-component solvent systems containing amides are interesting liquid systems for the study of molecular interactions as amides are the most common solvents used in chemical reactions and in many industrial processes. Moreover, amides are convenient model systems for the investigation of peptide and protein interactions in biological systems [1]. In previous papers [2], [3], [4], [5], [6], we have reported the studies on volumetric, acoustic and transport properties of binary mixtures containing amides. The present work is focused on the study of molecular interactions in binary mixtures of acetonitrile (ACN), with formamide (FA), N,N-dimethylformamide (DMF), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA), over the entire composition range at various temperatures. ACN molecules are aprotic but highly polar (μ = 3.7 D at T = 298.15 K) [7] with their dipoles oriented anti-parallel to each other and the strongly ordered structure in ACN is due to dipole–dipole interactions [7], [8], while the molecules of FA, DMF, NMA, and DMA are highly polar (μ = 3.37, 3.86, 4.39, and 3.72 D, respectively, at T = 298.15 K) [7]; FA and NMA are strongly associated through hydrogen bonding in the pure state [8] and this association decreases with increase in the number of methyl groups in the molecule. Thus, DMF and DMA are practically unassociated [9], [10]. A survey of literature indicates that there has been no temperature-dependent study of these systems from the point of view of their volumetric behaviour. Therefore, the present study is expected to reveal new and interesting results on molecular interaction in (ACN + amides) binary mixtures.

In the present paper, we report densities, ρ of (ACN + FA, or DMF, or NMA, or DMA), including those of pure liquids at atmospheric pressure and temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K, covering the entire composition range, expressed by the mole fraction x of ACN. The experimental values of ρ were used to calculate the excess molar volume, $V_{m}^{E}$ , and partial molar volumes, ${\bar{V}}_{m, 1}$ and ${\bar{V}}_{m, 2}$ . The variation of these parameters with composition and temperature of the mixtures has been discussed in terms of molecular interaction in these mixtures. The effect of the number and positions of methyl groups in these amides on molecular interactions has also been discussed.

Section snippets

Experimental

Acetonitrile and amides (FA, DMF, NMA, and DMA) used in the study were the products from s.d. fine chemicals, India and were purified by using the methods described in the literature [11], [12]; the mass fraction purities as determined by gas chromatography are: ACN > 0.996, FA > 0.995, NMA > 0.995, DMF > 0.997 and DMA > 0.997. Before use, the chemicals were stored over 0.4 nm molecular sieves for 72 h to remove water content, as far as possible, and were degassed at low pressure. The mixtures were

Results

The experimental results of density, ρ, measurements of binary mixtures of ACN with FA, DMF, NMA, and DMA, with ACN as a common component, over the whole composition range, expressed in mole fraction x of ACN (0 ⩽ x ⩽ 1), at different temperatures are listed in TABLE 2, TABLE 3, TABLE 4, TABLE 5. The excess molar volumes $V_{m}^{E}$ were calculated by using the following relation: $V_{m}^{E} = {xM}_{1} (1 / ρ - 1 / ρ_{1}) + (1 - x) M_{2} (1 / ρ - 1 / ρ_{2}),$ where M is the molar mass; subscripts 1 and 2 stand for pure components, ACN and amide,

Discussion

The results presented in TABLE 2, TABLE 3, TABLE 4, TABLE 5 and FIGURE 1, FIGURE 2, FIGURE 3, FIGURE 4 indicate that $V_{m}^{E}$ values are negative over entire mole fraction range and at all temperatures investigated for each binary system under study. The observed negative values of $V_{m}^{E}$ for (ACN + amide) mixtures indicate the presence of specific interactions between ACN and amide molecules. A plausible qualitative interpretation of the behaviour of these mixtures with composition has been suggested.

Conclusion

The densities for (ACN + FA or DMF or NMA or DMA) binary mixtures have been measured and the values of $V_{m}^{E}$ , ${\bar{V}}_{m, 1}$ , and ${\bar{V}}_{m, 2}$ were calculated. The $V_{m}^{E}$ values were found negative for all the mixtures and at each temperature studied, indicating the presence of specific interactions between ACN and amide molecules. The extent of negative deviations in $V_{m}^{E}$ values show that the interactions in these mixtures follow the order: FA > NMA > DMA > DMF. It is observed that the magnitude of $V_{m}^{E}$ depends upon the

Acknowledgements

The author is thankful to Department of Science and Technology (DST), New Delhi, India for financial support in form of SERC Fast Track Young Scientist Scheme. Thanks are also due to Prof. Anwar Ali, Head, Department of Chemistry, JMI, New Delhi for providing laboratory facility for the experimental work and to Dr. D. Jagannathan, Principal, Dyal Singh College, New Delhi for encouragement and providing computation facilities.

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Densities and volumetric properties of (acetonitrile + an amide) binary mixtures at temperatures between 293.15 K and 318.15 K

Abstract

Introduction

Section snippets

Experimental

Results

Discussion

Conclusion

Acknowledgements

J. Mol. Liq.

J. Chem. Thermodyn.

J. Chem. Eng. Data

Indian J. Technol.

Bull. Chem. Soc. Jpn.

Z. Phys. Chem.

Phys. Chem. Liq.

J. Sol. Chem.

Chin. J. Chem.

Int. J. Thermophys.

Indian J. Chem. A

Introduction to Liquid State Chemistry

Bull. Chem. Soc. Jpn.

J. Chem. Thermodyn.

Text Book of Practical Organic Chemistry

J. Phys. Chem.

Bull. Chem. Soc. Jpn.

J. Chem. Thermodyn.