Effect of placement of hydroxyl groups in isomeric butanediol on the behaviour of thermophysical and spectroscopic properties of pyrrolidin-2-one

doi:10.1016/j.jct.2004.11.020

The Journal of Chemical Thermodynamics

Volume 37, Issue 8, August 2005, Pages 791-801

https://doi.org/10.1016/j.jct.2004.11.020 Get rights and content

Abstract

The thermophysical parameters, viz. excess molar volume V^E, ultrasonic speed u, viscosity η and spectroscopic parameters, viz. IR and ¹H NMR have been measured for the mixtures of pyrrolidin-2-one and isomeric butanediol (1,2-, 1,3-, 1,4- and 2,3-BTD) over the whole composition range at 308.15 K. Results indicate that intermolecular interactions for different mixtures increase in the order: 2,3-BTD < 1,2-BTD < 1,3-BTD < 1,4-BTD. The partial and apparent molar quantities $Q_{i}^{E}$ , isentropic compressibility $K_{S}^{E}$ , excess viscosity η^E and excess Gibbs free energies of activation for viscous flow Δ_aG^∗E have also been estimated and analyzed. The spectroscopic measurements (IR and ¹H NMR) confirm that the interaction between unlike molecules takes place through hydroxyl groups of isomeric butanediol. A good agreement is obtained between excess quantities and spectroscopic data.

Introduction

Polyhydroxy compounds have number of applications in biochemical research because of there connection to biological system. These compounds are used as fogging agent in theatrical productions and are widely used in pharmaceuticals, cosmetics, petroleum, textile and other industries. More attention has been paid to study the physicochemical and thermodynamic properties of aqueous solution of polyhydroxy compounds. Thermophysical characterization of a system by experimental determination of properties such as excess molar volume, ultrasonic speed, viscosity and their composition variation are important tools to gain insight into solute-solvent interactions and packing effects of solute molecule in the stabilization/destabilization of a system [1], [2], [3], [4], [5], [6], [7], [8]. Czechowski et al. [9] and Nakanishi et al. [10] obtained excess molar volume of aqueous solution of different diols at different temperatures. Iloukhani and Bahram [11] carried out excess and partial molar volume measurements of aqueous solutions of 1,2-alkanediols at different temperatures. The results have been explained in terms of dissociation of the self-associated diol molecules and the formation of the aggregates between unlike molecules. The density and viscosity data of aqueous solutions of isomeric butanediol and poly(ethylene glycol)s have been reported by Teja and co-workers [12], [13]. Palepu and co-workers [14], [15] studied various properties of aqueous solutions of isomeric butanediol in order to analyze the interactions of butanediols with water in terms of placement of hydroxyl groups in isomeric butanediol molecules. Recently, George and Sastry [16] reported densities, viscosities, speed of sound and relative permittivities for (water + alkanediols) at different temperatures.

The study of isomeric butanediol (BTD) in non-aqueous media is also important from a fundamental point of view since it allows us to examine in detail the influence of spacing of the –OH groups on the thermodynamic properties of these compounds. In the present work, pyrrolidin-2-one (PY) is selected as a non-aqueous medium. The γ-butyrolactam (n = 5), i.e. PY is one of the cyclic amide which possess the basic (CO) and acidic (NH) group, in addition to high dipole moment. Cyclic amides are interesting compounds in which the nitrogen and carbon of a peptide bond are linked by a ring composed of methylene groups. These amide functional groups [17], [18], [19], [20] are structural part of peptide, polypeptide and proteins and constitute an important tool in the interpretation of numerous problems of molecular biology.

The excess molar volumes V^E, ultrasonic speed u, viscosity η and ¹H NMR and IR spectra have been measured for liquid binary mixtures of pyrrolidin-2-one and isomeric butanediol at 308.15 K temperature. The partial and apparent molar quantities $Q_{i}^{E}$ , isentropic compressibility $K_{S}^{E}$ , excess viscosity η^E, excess Gibbs free energies of activation for viscous flow Δ_aG^∗E and deviation in ¹H NMR chemical shift δ^E have been analyzed for the same mixtures. The aim of the work is to measure new data and to provide results for the characterization of the effect of placement of hydroxyl groups in BTD on the thermodynamic properties of PY. The results have been compared with aqueous based systems of diols and analyzed.

Section snippets

Materials

Pyrrolidin-2-one (>99 GC) and 1,2-butanediol (>98 GC) were obtained from Fluka and 1,3-butanediol (>99 GC), 1,4-butanediol (>99 GC) and 2,3-butanediol (>98 GC) were supplied by Merck. Pyrrolidin-2-one was dried with CaO and fractionally distilled as described elsewhere [21]. Diols were used as received. 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%. The purity of all the chemicals was

Results and discussions

Excess molar volumes V^E (cm³ · mol⁻¹), ultrasonic speed u (m · s⁻¹) and the absolute dynamic viscosities η (mPa · s) have been measured experimentally for the mixtures of pyrrolidin-2-one with isomeric butanediol at 308.15 K. The excess molar isentropic compressibilities $K_{S}^{E}$ , deviation in ultrasonic speed u^D, excess viscosity η^E and excess Gibbs free energies of activation for viscous flow, Δ_aG^∗E, were determined using the equation $K_{S}^{E} = K_{S} - K_{S}^{id},$ where $K_{S}^{id}$ can be expressed as follows: $K_{S}^{id} = \sum_{i} x_{i} [(K_{S, i}^{*}) + T (A_{P, i})]$

Acknowledgement

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

References (32)

S.L. Oswal et al.
Fluid Phase Equilibr.
(1998)
S. Martinez et al.
Fluid Phase Equilibr.
(2000)
S.K. Mehta et al.
Fluid Phase Equilibr.
(2002)
P. Pirila-Honkanen et al.
Thermochim. Acta
(1989)
G.R. Hedwig
J. Chem. Soc., Faraday Trans.
(1993)
S. Cabani et al.
J. Chem. Soc., Faraday Trans.
(1981)
M.A. Schwitzer et al.
J. Chem. Eng. Data
(1998)
M.J.A. Barbas et al.
Phys. Chem. Chem. Phys.
(2000)
H.L. Zhang
J. Sol. Chem.
(2003)
S. Czerkas et al.
Phys. Chem. Liq.
(1998)

G. Czechowski et al.

J. Chem. Eng. Data

(1988)

K. Nakanishi et al.

J. Phys. Chem.

(1967)

H. Iloukhani et al.

Phys. Chem. Liq.

(2000)

T. Sun et al.

J. Chem. Eng. Data

(1992)

R.J. Lee et al.

J. Chem. Eng. Data

(1990)

B. Hawrylak et al.

J. Sol. Chem.

(1998)

Cited by (20)

Densities and volumetric properties of binary mixtures of 2-ethoxyethanol with 2-pyrrolidinone and N-methylacetamide from 303.15 to 323.15 K
2023, Journal of Chemical Thermodynamics
Citation Excerpt :
The existence of etherial oxygen augments the ability of –OH group of the same molecule to form hydrogen bonds with the other unlike molecules. 2-Pyrrolidinone (2-Pyrrol) is a highly polar aprotic solvent with low volatility extensively used in the field of applied chemistry, industry and biochemical processes [8,9]. 2-Pyrrolidinone, a five-member cyclic amide can serve as a simple model to study the dynamics of hydrogen bonded molecular systems.
The densities ρ of the binary mixtures of 2-ethoxyethanol with 2-pyrrolidinone and N-methylacetamide have been reported over the entire range of compositions at temperatures from 303.15, 313.15 and 323.15 K and atmospheric pressure. Using the experimental density data, the excess molar volume, $V_{m}^{E}$ , partial molar volumes ( ${\bar{V}}_{m, 1}$ and ${\bar{V}}_{m, 2}$ ) and excess partial molar volumes ( ${\bar{V}}_{m,1}^{E}$ and ${\bar{V}}_{m,2}^{E}$ ) were determined. The variations of excess molar volume with composition and temperature were found to be negative indicating the presence of specific intermolecular interactions between 2-ethoxyethanol and 2-pyrrolidinone/N-methylacetamide molecules. The observed variations of partial molar volumes and their derivatives provide a basis for extending our understanding of molecular interactions with respect to temperatures in these binary liquid mixtures.
Effect of position of OH group in isomeric butanediols on intermolecular interaction with Choline Acetate: A thermodynamic study at different temperatures
2021, Journal of Molecular Liquids
The prominent effect of the position of hydroxyl groups in isomeric butanediols i.e.1,3-butanediol (1,3-BTD), 1,2-butanediol (1,2-BTD) and 2,3-butanediol (2,3-BTD) on intermolecular interactions with Choline Acetate has been investigated using various thermophysical parameters such as density $ρ$ , speed of sound u, refractive index $n_{D}$ and specific conductivity κ over different concentration range and at temperatures varying from 293.15 to 323.15 K at atmospheric pressure. To gain further insight the derived parameters such as apparent molar volumes $V_{ϕ}$ , apparent molar isentropic compressibilities $K_{s ϕ}$ , and their infinite parameters mainly limiting apparent molar volumes at infinite dilution $V_{ϕ}^{o}$ , limiting apparent molar expansibilities $E_{ϕ}^{o}$ , limiting isentropic compression $K_{ϕ}^{o}$ , molar refraction $R_{m}$ and infinite molar conductance $̂_{m}^{o}$ values have been calculated. The least values obtained for apparent molar volumes and compressibilities in case of 1,3-BTD mixtures are attributed to its highest ability to form intramolecular hydrogen bonding among isomeric butanediols and thus lesser availability to interact with Choline Acetate molecules. However for 2,3-BTD and 1,2-BTD binary mixtures the results have been explained on the basis of hydrophobic or iceberg effect where alkyl groups are present either on one end (1,2-BTD) or at both ends (2,3-BTD) while OH groups are located at vicinal carbon atoms.
Density of water - 2-pyrrolidone mixture a new vibrating tube densimeter from (278.15–323.15) K and up to 70 MPa
2021, Journal of Molecular Liquids
Citation Excerpt :
The structure of 2-pyrrolidone is also of great interest, since its functional amide groups are an integral part of peptides, polypeptides and proteins, and its self-association serves as a model for hydrogen bonding in nucleic acid amides. These aspects represent an important tool in the interpretation of many problems in molecular biology [5]. Pure pyrrolidone is capable of strong self-association through the Hbond (>CO ··· HN) [6–10] but there are different opinions about the nature of this process.
The present work deals with a measurement system for densities of compressed liquids over the temperature range of 263–473 K and pressure up to 70 MPa. The functionality of the installation is based on the usage of a commercial vibrating tube densimeter DMA HP. Calibration of the DMA HP cell was performed by two methods in which a vacuum, water, toluene, and aqueous solution of NaCl were used as calibration fluids. The density at high pressures of 2-pyrrolidone was measured in the range of 0.1–70 MPa at two different temperatures (308.15 and 323.15) K, and that of water-2-pyrrolidone mixture was measured in the entire composition range of the mixture liquid state in the range of 0.1–70 MPa at five different temperatures - from (278.15 to 323.15) K. Density data were fitted by Tait-type equation where the absolute average percentage deviation between measured and calculated densities was about 0.02%. These data were later used to calculate the excess molar volumes, $V_{m}^{E}$ , partial molar volumes of water, $V_{1}$ and 2-pyrrolidone $V_{2}$ , and to obtain the limiting partial molar volumes of components $V_{i}^{\infty}$ . Structure–property relationships were analyzed, the effects of temperature and pressure on these properties were also discussed.
Thermodynamic and spectroscopic studies of intermolecular interactions between isoamyl alcohol and monocyclic aromatic non-ideal binary liquid mixtures
2020, Chemical Data Collections
Citation Excerpt :
H-bonding interaction > OH- interaction > molecules fitting interaction 1H-NMR can provide meaningful physical information about structural and molecular interactions [60,61]. The 1H-NMR chemical shift value is inversely proportional to the electron density around a proton.
The thermodynamic properties such as excess volume (V^E), excess Gibbs free energy (G*^E), deviation in viscosity (Δη) and deviation in isentropic compressibility (Δκ_s) have been calculated using the experimental data of density (ρ), viscosity (η) and speeds of sound (u) values of binary mixtures namely; isoamyl alcohol (IAA) + chlorobenzene (CB), + benzonitrile (BN), + aniline (AL), + benzaldehyde (BZ) and + nitrobenzene (NB) over the entire range of mole fraction at temperature 298.15, 303.15 and 308.15 K and under atmospheric pressure. The obtained results were fitted to the Redlich-Kister (R-K) equation to determine the adjacent binary coefficients with errors. The calculated parameters were discussed in terms of intermolecular interactions such as H-bonding, OH-π, and molecules fitting interactions in the non-ideal solutions. Further, the pure liquids and their mixture concentrations were characterized by FT-IR, and ¹H-NMR spectral technologies and using these spectral results elucidate intermolecular interaction (H-bond) in dissimilar molecules.
Effect of temperature and position of OH group in isomeric butanediols in intermolecular interactions with 2-chloroaniline: A thermodynamic, DFT and molecular dynamics approach
2020, Journal of Molecular Liquids
Citation Excerpt :
Glycols have widespread applications in aviation, textile, food, medicine, automotive surface coatings, explosives, petroleum industries [21–23]. The thermo-dynamical and theoretical interaction analysis of 2-chloroaniline and isomeric butanediol with different non-aqueous liquids have been extensively studied [24–30]. This work describes the experimental and theoretical investigations of the significant influence on the positional changes of –OH group and its impact on the intermolecular interaction between 2-chloroaniline and butanediol mixtures.
The pronounced effect of the position of the hydroxyl groups in isomeric butanediols (1, 2-butanediol (12BDL), 1, 3-butanediol (13BDL) and 1, 4-butanediol (14BDL)) in the formation of hydrogen bonds with 2-chloroaniline (2CA) was investigated by using experimental and computational methods. The density ( $ρ$ ) and speed of sound ( $u$ ) in binary mixture was determined at T = (303.15–318.15) K and at atmospheric pressure p = 0.1 MPa. Values of excess molar volume ( $V_{m}^{E}$ ), and excess isentropic compressibility ( $k_{s}^{E}$ ) were determined by using experimental data. It was observed that these excess properties ( $V_{m}^{E}$ $k_{s}^{E}$ ) departs negatively from the ideal mixture which indicates the formation of intermolecular hydrogen bonds. The volumetric properties like excess partial molar volume ( ${\overline{V}}_{m, 1}^{E}$ ${\overline{V}}_{m, 2}^{E}$ ), partial molar volume ( ${\overline{V}}_{m, 1}^{0}$ , ${\overline{V}}_{m, 2}^{0}$ ₎ and excess partial molar volume ( ${\overline{V}}_{m, 1}^{0 E}$ ${\overline{V}}_{m, 2}^{0 E}$ ) are derived at infinite dilutions. Quantum mechanical approach was used to study the intermolecular hydrogen bond interactions in self and cross-associated complexes of 2-chloroaniline and isomeric butanediols with the aid of DFT in the gas phase, while classical molecular dynamic simulations were carried out in the liquid phase. Experimental, quantum mechanical and classical molecular dynamic methods are used to investigate the formation of a hydrogen-bonded network between 2-chloroaniline and isomeric butanediols mixtures. The investigated results were further confirmed by the existence of hydrogen bonding evolution between 2-chloroaniline and isomeric butanediols through FT-IR Spectral studies. The Fourier transform Infrared spectroscopic data strongly confirms and support the existence of intermolecular hydrogen bonding and molecular associations between component molecules.
Densities, ultrasonic speeds, excess and partial molar properties of binary mixtures of 2-pyrrolidone with isomeric propanediols at temperatures from 303.15 K to 323.15 K
2017, Journal of Chemical Thermodynamics
The densities, ρ and speeds of sound, u of the binary mixtures of 2-pyrrolidone with 1,2-propanediol and 1,3-propanediol, including those of pure liquids, have been measured over the entire range of composition at temperatures, (303.15–323.15) K and atmospheric pressure. Using the experimental data, excess molar volumes, $V_{m}^{E}$ , excess isentropic compressibility, $κ_{s}^{E}$ , excess speeds of sound, $u^{E}$ and excess molar isentropic compressibility, $K_{s,m}^{E}$ were calculated. The partial molar volumes, ${\bar{V}}_{m, 1}$ and ${\bar{V}}_{m, 2}$ , partial molar isentropic compressibilities, ${\bar{K}}_{s,m, 1}$ and ${\bar{K}}_{s,m, 2}$ , excess partial molar volumes, ${\bar{V}}_{m, 1}^{E}$ and ${\bar{V}}_{m, 2}^{E}$ and excess partial molar isentropic compressibilities, ${\bar{K}}_{s,m, 1}^{E}$ and ${\bar{K}}_{s,m, 2}^{E}$ over whole composition range; partial molar volumes, ${\bar{V}}_{m, 1}^{°}$ and ${\bar{V}}_{m, 2}^{°}$ , partial molar isentropic compressibilities, ${\bar{K}}_{s,m, 1}^{°}$ and ${\bar{K}}_{s,m, 2}^{°}$ , excess partial molar volumes, ${\bar{V}}_{m, 1}^{° E}$ and ${\bar{V}}_{m, 2}^{° E}$ and excess partial molar isentropic compressibilities, ${\bar{K}}_{s,m, 1}^{° E}$ and ${\bar{K}}_{s,m, 2}^{° E}$ of the components at infinite dilution have also been calculated. The results have been discussed in terms of intermolecular interactions prevailing in these mixtures. The results indicated that the interactions in these systems follow the order: 1,2-propanediol > 1,3-propanediol. The speeds of sound of these mixtures have been analysed by using scaled particle theory and the results are compared with experimental findings.

View all citing articles on Scopus

View full text

Effect of placement of hydroxyl groups in isomeric butanediol on the behaviour of thermophysical and spectroscopic properties of pyrrolidin-2-one

Abstract

Introduction

Section snippets

Materials

Results and discussions

Acknowledgement

Fluid Phase Equilibr.

Fluid Phase Equilibr.

Fluid Phase Equilibr.

Thermochim. Acta

J. Chem. Soc., Faraday Trans.

J. Chem. Soc., Faraday Trans.

J. Chem. Eng. Data

Phys. Chem. Chem. Phys.

J. Sol. Chem.

Phys. Chem. Liq.

J. Chem. Eng. Data

J. Phys. Chem.

Phys. Chem. Liq.

J. Chem. Eng. Data

J. Chem. Eng. Data

J. Sol. Chem.