Thermodynamic, transport, and spectroscopic studies for mixtures of isomeric butanediol and N-methyl-2-pyrrolidinone

doi:10.1016/j.jct.2009.06.006

The Journal of Chemical Thermodynamics

Volume 41, Issue 12, December 2009, Pages 1329-1338

https://doi.org/10.1016/j.jct.2009.06.006 Get rights and content

Abstract

The thermodynamic parameters viz. excess molar volume V^E and speed of sound u, transport parameter viscosity η, and spectroscopic parameters viz. IR, ¹H, ¹³C NMR have been measured for the mixtures of isomeric butanediol (1,2-, 1,3-, 1,4-, and 2,3-butanediol) and N-methyl-2-pyrrolidinone over the whole composition range at 308.15 K. The partial molar quantities $Q_{i}^{E}$ , isentropic compressibility $K_{S}^{E}$ , viscosity deviation Δη, deviation in Gibbs free energies of activation for viscous flow g(x), and excess NMR chemical shift δ^E have been estimated and analyzed. Results show that the interaction between unlike molecules takes place through hydroxyl groups of isomeric butanediol and 2 bonds on the lefthand side CO group of N-methyl-2-pyrrolidinone. Excellent agreement between thermodynamic and spectroscopic measurements is observed.

Introduction

Amide association constitutes a simple model system for base pairing in nucleic acids as well as for peptide bond interactions in polypeptides and proteins. Particularly interesting are cyclic amides (lactams) in which the nitrogen and carbon atoms of the peptide bond are composed by a ring composed of methylene groups. Cyclic amides in general are high density, high boiling point, and high polarity solvents. They are completely miscible over the entire composition range with water. 2-Pyrrolidinone and its methyl derivative, that is, N-methyl-2-pyrrolidinone have been used as cosolvent in the petroleum industry to increase the selectivity and solvent power for extracting aromatic hydrocarbons and have excellent thermal and chemical stability [1], [2], [3], [4], [5], [6], [7], [8]. García et al. [1] have determined excess volumes, mixing viscosities, and excess Gibbs free energies of activation of viscous flow of the aqueous binary mixtures of the amides formamide, N-methylformamide, N,N-dimethylformamide, pyrrolidin-2-one, and N-methyl-2-pyrrolidinone from density and viscosity measurements. The values of these functions point to strong amide–water interaction with the formation of a variety of aggregates, the nature of which depends on the extent of substitution of the amides. George and Sastry [3] reported experimental densities, viscosities, speeds of sound, and relative permittivities, for three binary mixtures of (water + 2-pyrrolidinone, +N-methyl-2-pyrrolidinone, and +N-vinyl-2-pyrrolidinone) over the entire composition range and at different temperatures. The analysis revealed that both hydrophobic and hydrophilic hydrations are responsible for the complex nature of the thermophysical behavior in these mixtures. Densities and viscosities for binary mixtures of N-methyl-2-pyrrolidinone with cyclohexane, benzene, toluene, p-xylene, and ethylbenzene at different temperatures and atmospheric pressure have been reported by Yang et al. [7], [8], [9]. The molecular interactions between N-methyl-2-pyrrolidinone and aromatic hydrocarbons have been analysed by Liu and coworkers [10]. Recently, Dávila and Trusler [11] reported thermodynamic properties of mixtures of N-methyl-2-pyrrolidinone and methanol. It is anticipated that there is a propensity to form hydrogen bonds between each lone pair of electrons on the oxygen atom in the N-methyl-2-pyrrolidinone molecules and a methanol molecule.

Alkanediols are the simplest and model structural units for polyhydroxy compounds. These compounds play a significant role in industry due to their wide range of practical applications, such as antifreezes, coolants, aircraft deicing fluids, heat transfer fluids, hydraulic fluids, solvents, food, flavor and fragrances, pharmaceuticals, chemical intermediates, plasticizers, thermoset plastic formulations, petroleum, textile, and other industries. The structural and interactional analysis of alkanediols in water mixtures has been extensively studied [12], [13], [14], [15], [16], [17], [18]. Nakanishi et al. [12] obtained excess molar volume of aqueous solutions of different diols and it has been found that the volumetric behavior of α,ω-alkanediols is almost same, although their V^E slightly increases with molecular size. However, if one of –OH group is not located at the end of diol molecule, the interstitial contribution due to possible cavity occupation by methyl group result in a large volume loss. Palepu and coworkers [16], [17] have reported various thermophysical properties of aqueous solutions of isomeric butanediol to study the influence of change in the relative –OH positions along the alkyl chain of isomeric butanediol in water. George and Sastry [18] reported densities, viscosities, speed of sound, and relative permittivities for water + alkanediols and found that the water molecule with diols results less overall volume indicating that structure-making effects are prevalent in aqueous solution of diols. Results show that α,ω-alkanediols facilitate heteroatomic hydrogen bonding between water and diol, whereas, terminal hydrophobic –CH₃ groups induced the compression effects in surrounding water molecules.

Alkanediol-amide mixed solvents constitute interesting binary liquid systems, however fewer experimental data are available [19], [20], [21]. As a part of our research program of measuring physicochemical properties of diols in amides [22], [23], [24], [25], [26], we report thermodynamic, transport and spectroscopic parameters of isomeric butanediol (BTD) in N-methyl-2-pyrrolidinone (NPY). The results have been compared with mixtures of diols in N,N-dimethylformamide (DMF)/pyrrolidin-2-one (PY)/water and analyzed.

Section snippets

Materials

N-methyl-2-pyrrolidinone (NPY; >99 g.c.) and 1,2-butanediol (1,2-BTD; >98 g.c.) obtained from Fluka and 1,3-butanediol (1,3-BTD; >99 g.c.), 1,4-butanediol (1,4-BTD; >99 g.c.) and 2,3-butanediol (2,3-BTD; >98 g.c.) were purchased from Merck. N-methyl-2-pyrrolidinone was dried with CaO and fractionally distilled as described elsewhere [27]. Prior to use, all the chemicals were stored over molecular sieves to remove any traces of water. The water impurity in the chemicals was as low as <0.005 mol%. The

Thermodynamic properties

The experimentally measured excess molar volume V^E values for mixtures of NPY and BTD at 308.15 K are summarized in table 2 and graphically presented in figure 1. The V^E values are negative for 1,2-BTD and 1,4-BTD and both positive and negative for 1,3-BTD and 2,3-BTD. These results show strong hydrogen bonding between 2 bonds on the lefthand side C double bond O group of NPY and –OH groups of diols in the case of 1,2-BTD and 1,4-BTD. In our earlier reports on 1,4-BTD and 1,2-BTD in PY [22] and DMF [23], it was observed that 1,4-BTD

Conclusions

Strong interactions between NPY and BTD mixtures have been analyzed by their thermodynamic and transport properties. The position of hydroxyl groups caused a noticeable effect on thermophysical properties. 1,2-BTD and 1,4-BTD interacts more effectively with NPY than 1,3-BTD and 2,3-BTD. On the basis of spectroscopic measurements, it is concluded that these interactions are through the 2 bonds on the lefthand side C double bond O group of NPY and the –OH groups of the diols. The results obtained from spectroscopic measurements correlate

Acknowledgement

The authors wish to thank the UGC (India) for financial assistance.

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Thermodynamic, transport, and spectroscopic studies for mixtures of isomeric butanediol and N-methyl-2-pyrrolidinone

Abstract

Introduction

Section snippets

Materials

Thermodynamic properties

Conclusions

Acknowledgement

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Phys. Chem. B

J. Chem. Soc., Faraday Trans.

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Phys. Chem.

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Chem. Thermodyn.

J. Phys. Chem.

J. Chem. Thermodyn.