Alkanol Mixtures Research Articles

Exploring Structure–Property Relationships in Eucalyptol and 1-Alkanol Mixtures: A DFT and Experimental Study

Exploring Structure–Property Relationships in Eucalyptol and 1-Alkanol Mixtures: A DFT and Experimental Study

Integrated exploration of intermolecular interactions in 3-methyl-1-butanol and C5-C8 1-alkanol mixtures via density functional theory and experimental approaches

The investigation provides a study on the thermophysical properties of 3-methyl-1-butanol with medium-chain alcohols (1-pentanol to 1-octanol) within the temperatures 293.15 K to 333.15 K. Findings indicate positive excess molar volumes that escalate with the lengthening of the carbon chain in the alcohols. Viscosity measurements demonstrate negative deviations from ideality, which are accentuated with longer alkyl chains. The analysis suggests that intermolecular forces between 3-methyl-1-butanol and alcohols are weak. Furthermore, the study uses the Cubic Plus Association (CPA) model to establish a relationship between the densities of the mixtures, demonstrating a close match with data obtained through experimentation. The CPA model deviates by a maximum of 0.53 % and indicates the model's reliability in portraying real-world data. Furthermore, this study entails a density functional theory (DFT) investigation of hydrogen bonding among 3-methyl-1-buthanol + 1-alkanol. The analysis encompasses properties including interaction energies, geometrical parameters, nuclear magnetic resonance (NMR) analyses, atoms in molecules analysis (AIM), natural bond orbital analysis (NBO), and excess volume. Our calculations reveal the strongest hydrogen bonding occurs in mixtures of 3-methyl-1-butanol and 1-pentanol, while the weakest interactions form in mixtures of 3-methyl-1-butanol and 1-octanol. Notably, calculated data on hydrogen bonding between 3-methyl-1-buthanol and 1-alkanols align with experimental findings, underscoring the agreement between computational and empirical approaches.

Modeling and measurement of density and viscosity of ethyl Lactate + 1-alkanol mixtures

In the current paper, the aim is to investigate the characteristics and relationships of liquid mixtures containing ethyl lactate and 1-Alkanols (C4–C7), which include 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol. To accomplish this, excess molar volumes and the deviation in viscosity were determined by utilizing experimental density and viscosity measurements at different temperatures and a pressure of 0.1 MPa. Our findings revealed that for solutions containing ethyl lactate and 1-butanol or 1-pentanol, positive values were observed when the mole fractions were higher in alcohols and lower in lactate. However, as the mole fractions shifted towards higher levels of lactate, the excess molar volumes became negative. On the contrary, when examining binary solutions of ethyl lactate with 1-hexanol and 1-heptanol, positive values for the excess molar volumes were found. The PC-SAFT model was used to simulate the density of pure fluids and liquid mixtures, resulting in a maximum deviation of 1.17 % for ethyl lactate and 1-hexanol solutions. Our analysis revealed that PC-SAFT is capable of accurately predicting and correlating the density of both pure liquids and solutions.

Analyzing Intermolecular Interactions in 2-Methyl-1-pentanol and C4-C7 1-Alkanol Mixtures: Thermodynamic and Transport Investigations

Analyzing Intermolecular Interactions in 2-Methyl-1-pentanol and C4-C7 1-Alkanol Mixtures: Thermodynamic and Transport Investigations

Thermodynamic and molecular simulation analysis of molecular interactions between methyl 2–hydroxyisobutyrate + water or n–alkanol (C1–C2) mixtures

Methyl 2–hydroxyisobutyrate (HBM) is essential as a photoresist thinner in semiconductor fabrication. In this study, we examined the density and viscosity of HBM combined with water or alkanol (C1–C2) at a pressure of 0.1 MPa and temperatures ranging from 288.15 K to 323.15 K. Based on experimental data, we calculated the excess molar volume, as well as apparent, partial, and excess partial molar volumes, and deviations in viscosity. These derived thermodynamic properties were then modeled using the Redlich-Kister (RK) polynomial equation. The VmE values of HBM + water mixtures are more negative compared to HBM + alkanol mixtures because of the stronger H–bonding interactions in HBM–water than in HBM–alkanol. With increasing temperature, the VmEbecome more negative, whereas the Δη values lower with a temperature rise. The values for excess molar volume and deviation in viscosity were analyzed through a graph theoretical method. Additionally, the excess free energy of activation was determined from the viscosity data. FTIR spectral analysis validated the findings related to intermolecular interactions and the graph theoretical method. Lastly, molecular dynamics simulations shed light on the intermolecular interaction energies and their differences in the studied binary systems.

Theoretical and experimental study of triethanolamine and 1-alkanol mixtures

Theoretical and experimental study of triethanolamine and 1-alkanol mixtures

Thermodynamic study of mesitylene + alkanol mixtures: Insights into molecular interactions

Excess properties are a powerful tool for understanding the intermolecular interactions in mixtures. In this study, the excess molar volume (VmE), excess isentropic compressibility (κsE) deviation in ultrasonic speed (Δu), and refractive index (ΔnD) were analyzed for mixtures of mesitylene and alkanol to interpret their intermolecular interactions. Our findings demonstrate that positive values of VmE and κsE indicate the predominance of the rupture of H-bonding in self-associated alkanol dominate over the electron donor–acceptor interaction between the hydroxyl group of alkanol and π–electrons of mesitylene. It was also observed that these electron donor–acceptor interactions weaken as the temperature increases. These observations were further supported by the behavior of molecular association parameter (MA), free intermolecular length, and available volume. Among the alkanols studied, n-butanol exhibited the highest value of MA, suggesting a strong degree of molecular association due to favorable intermolecular interactions between the dissimilar molecules. In contrast, sec-butanol showed the lowest value, which can be attributed to the steric hindrance caused by three methyl groups of mesitylene and the two methyl groups attached to a hydroxyl carbon atom in sec-butanol. Regarding correlation, Schaffs collision factor theory demonstrated high predictive power for ultrasonic speed compared to other models.

Thermophysical properties of N-isopropyl-2-propanamine+alkanol (C1-C3) mixtures as absorbents for carbon dioxide capture

Thermophysical properties of N-isopropyl-2-propanamine+alkanol (C1-C3) mixtures as absorbents for carbon dioxide capture

Thermophysical properties of 2-amino-2-methylpropan-1-ol + alkanol mixtures: Investigation of molecular interactions by insight of FT-IR spectroscopy

We report the experimental data of dynamic viscosity (η) and ultrasonic speed (u) for 2-amino-2-methylpropan-1-ol (AMP) (1) + alkanol (C1-C3) (2) at T = (298.15–318.15) K and 0.1 MPa pressure. The derived excess (or deviation in) properties like dynamic viscosity (Δη), speed of sound (Δu) and excess isentropic compressibility (κSE) were regressed through Redlich-Kister polynomial equation. The Δη values were analyzed in terms of an Ab-initio approach, to study the intermolecular interactions between the binary components. Our analysis indicated that compared to propanol, methanol and ethanol interact strongly with AMP and 2-propanol exhibited the weakest interactions with AMP owing to steric hindrance by branched propyl group. In addition, viscosity (η) values and ultrasonic speed (u) data were analyzed using the various thermodynamic models/correlations that agreed well with our experimental data. Furthermore, we analyzed the FT-IR spectra of pure components and their binaries and observed prevailing hydrogen bonding interactions between the N-atom and OH-group of AMP with the OH-group of alkanol. Our findings highlight the great bonding capability of AMP with lower alkanol due to its small size and linear shape and can provide information on designing effective binary mixtures (blended) solvents based on AMP for CO2 absorption.

Study of Nonideality Behavior of p-Methylacetophenone and 1-Alkanol Mixtures from Measurement and Modeling of Density and Viscosity

The aim of this work is to investigate experimentally and theoretically thermophysical properties (density and viscosity) and derived properties (excess molar volume and viscosity deviation) of p-methylacetophenone + alkanols (C5 to C9) in the range of 293.15 to 323.15 K and a pressure of 0.1 MPa. The properties studied were density, viscosity, excess molar volume, and deviation in viscosity. To model the density of the liquid mixtures, we used the perturbed chain-statistical associating fluid theory equation of state (PC-SAFT EoS) and the volume translated Peng-Robinson-Stryjek-Vera equation of state (VTPRSV EoS). Using a correlation approach an overall deviation of 0.34% and 0.28% was obtained, respectively, while good predictive results were obtained (0.44% using PC-SAFT EoS and 0.46% using VTPRSV EoS). Also, we use two correlations without fitted parameters (Kendall-Munroe correlation and Nguyenhuynh correlation) to model the experimental viscosity and obtained an overall deviation of 5.07% and 3.07%. In addition, the Redlich–Kister correlation (with three fitted parameters) was able to correctly correlate the excess molar volume and the deviation in viscosity for all mixtures. Finally, the results obtained from the work have been discussed in terms of the nature of molecular interactions between the components of the p-methylacetophenone + alkanol mixture.

Study of Thermodynamic and Transport Properties of Formamide and 1-Alkanol Mixtures at Different Temperatures

Study of Thermodynamic and Transport Properties of Formamide and 1-Alkanol Mixtures at Different Temperatures

Measurement of the Density and Viscosity of Diisopropyl Ether and 1-Alkanol Mixtures at Various Temperatures

Measurement of the Density and Viscosity of Diisopropyl Ether and 1-Alkanol Mixtures at Various Temperatures

Experimental Study and Modeling Using the PFP Theory and the ERAS Model of the Excess Molar Volume and Isentropic Compressibility of Dimethylbenzylamine with Alkanol Mixtures at Different Temperatures

Experimental Study and Modeling Using the PFP Theory and the ERAS Model of the Excess Molar Volume and Isentropic Compressibility of Dimethylbenzylamine with Alkanol Mixtures at Different Temperatures

Thermodynamic Studies on Non-ideal Binary Mixtures of Isoamyl Alcohol and Various Alkanols at 298.15 to 308.15 K

Experimental values of density (ρ), viscosity (η) and speed of sound (u) of five non-ideal binary {solvent + co-solvent} liquid mixture systems, namely isoamyl alcohol (IAA) + ethanol (EA), isoamyl alcohol + 1,2-ethanediol (EDO), isoamyl alcohol + 1,3-propanediol (PDO), isoamyl alcohol + 1,4-butanediol (BDO) and isoamyl alcohol + glycerol (GLY) have been measured over the whole composition range of mole fraction at T = (298.15–308.15) K with 5 K temperature intervals under atmospheric pressure. According to the ρ, η, and u data, the values of excess volume (VE), deviation in viscosity (∆η), and deviation in isentropic compressibility (∆κs) were calculated. The negative values of VE and ∆κs and positive values of Δη obtained for the studied binary liquid systems are indicative of strong intermolecular interactions between unlike molecules. Further, the effects of the number of –OH groups in polyols, as well as the influence of temperature on thermodynamic parameters, were analyzed. Furthermore, the calculated values of VE, ∆η, and ∆κs were correlated with the Redlich–Kister (R–K) model and reasonable standard deviations were obtained.

A combined experimental and theoretical study on diglyme + 1-alkanol liquid mixtures

The properties, structuring and intermolecular forces of diglyme + alkanol mixtures are studied using a combined experimental and theoretical approach. The thermophysical properties as well as the molecular simulation results provide detailed characterization of the mixtures in terms of composition, type of 1-alkanol and temperature. The possibility of development of heteroassociations by glyme - alkanol hydrogen bonding as well as their effect on the weakening and breaking on alkanols self-association show a pivotal role on the mixtures structure as well as the glyme self-association. The reported mixtures show complex structural effects varying with mixtures composition which may be considered as model of ether – hydroxyl interaction and their effects on the mixture’s properties and nature.

On the properties of N-methyl-2-pyrrolidonium hydrogen sulfate ionic liquid and alkanol mixtures

The properties of N-methyl-2-pyrrolidonium hydrogen sulfate mixed with alkanols are studied as a function of mixtures composition and temperature. Experimental physicochemical properties combined with molecular simulation (quantum chemistry and classical molecular dynamics) were considered, thus providing a micro and macroscopic characterization of fluids' structuring, intermolecular forces and molecular aggregation. The results were analyzed in thermodynamics terms considering deviations of ideality and mixing properties as well as from the coordination and interaction between the involved ions and molecules by the developed complex hydrogen bonding networks. The results allow a multiscale characterization of the considered mixed systems thus providing the required information for the possible applications of low viscous protic pyrrolidonium-based ionic liquids and their mixtures with relevant hydrogen bonding molecular cosolvents.

Accounting for quadrupolar interactions in the CPA equation of state: A modelling approach for binary mixtures of CO2 or benzene with n-alkanes and 1-alkanols

The Cubic Plus Association (CPA) equation of state (EoS) is extended with the theory for quadrupolar molecules of Gross, yielding the CPA-G model. CPA-G is compared to the recently developed qCPA, which uses the polar theory of Larsen and coworkers. Each model requires an additional adjustable parameter for quadrupolar molecules.The models are evaluated by means of their ability to model the phase equilibria of binary mixtures of CO2 or benzene with n-alkanes and 1-alkanols, as well as binary mixtures of quadrupolar molecules. A refined technique of accounting for cross-association in the CO2 + 1-alkanol systems is proposed, allowing an improved description of these systems without the use of a binary interaction parameter. Accounting for cross-association in the benzene + 1-alkanol systems investigated in this work did not lead to improved results. Both CPA-G and qCPA provide significant improvements over nonpolar CPA in both n-alkane and 1-alkanol mixtures, with excellent results obtained in the subcritical region without the use of binary interaction parameters. qCPA continues to provide excellent predictions in the supercritical region, while CPA-G overestimates the solubility pressures in the supercritical region. Both quadrupolar models can qualitatively predict the existence of three-phase equilibrium in the CO2 + n-alkane and CO2 + 1-alkanol systems. The simple combining rules used for cross-quadrupolar interactions in both CPA-G and qCPA do not take molecular orientation into account and are unable to truly capture the phase behaviour in the CO2 + benzene system.

Densities and Viscosities of Binary Mixtures Containing Methyl Isobutyl Ketone and (C6–C10) 1-Alkanol

In the present study, to identify the governing intermolecular interactions in the binary mixtures of methyl isobutyl ketone (MIBK) and 1-alkanols (1-hexanol up to 1-decanol), experimental values o...

Thermo-physical and spectral investigations of binary liquid mixture of 2-(2-butoxyethoxy) ethanol with alcohols at temperature range of 293.15 K to 313.15 K

In continuation to our prior investigational studies on the interactions between binary mixtures of alkoxy alkanols and alcohols, here, we report density, speed of sound, FT-IR as well as NMR analysis of 2-(2-butoxyethoxy) ethanol, CH3(CH2)3OC2H4O(CH2)2OH, viz., 1-propanol CH3(CH2)2OH, 2-propanol (CH3)2CHOH, 1-butanol CH3(CH2)3OH and 2-butanol CH3CH2CH(OH)CH3. The experimental data of densities and speeds of sound over the entire composition range at 293.15, 298.15, 303.15, 308.15 and 313.15 K were used to calculate the values of excess functions and deviations in properties. Utilizing the spectroscopic analysis, chemical shift/frequency was accounted. The evaluated properties from experimental data have been construed in terms of the difference in the size of the molecule as well as the strength of specific and non-specific interactions between components of the mixture. The excess functions and their deviations have also been correlated using Redlich-Kister type polynomial equation by the method of least-squares for the estimation of the binary coefficients and the standard deviations.

Methanol-ethanol “ideal” mixtures as a test ground for the computation of Kirkwood-Buff integrals

Mixtures of 1-alkanols are a textbook example of the concept of ideal mixtures. Yet, such mixtures have a very strong local order due to the hydrogen bonding interactions, with a strong tendency for chain formation. Despite this apparent non-ideality, the Kirkwood-Buff integrals of such system exhibit near ideal behavior. This dual property can be used to test the calculations of the Kirkwood-Buff integrals in a controlled mixing situation, and clarify many points, in particular the statistical problems that can be encountered. By studying the methanol-ethanol mixtures, we uncover an interesting physical asymmetry between low methanol and low ethanol concentrations, which can produce statistical artifacts in the calculation of Kirkwood-Buff integrals, illustrating and exemplifying some of the difficulties encountered in such calculations. Finally, liquid state integral equations results for these mixtures are reported. They help demonstrate that thermodynamic ideality hides complex correlations and microscopic non-ideality.