Binary Mixtures Of Alcohols Research Articles

Thermodynamic and spectroscopic analyses of N-Methyl benzylamine-isomeric amyl alcohol binary mixtures: Jouyban-Acree model correlation and experimental validation

ABSTRACT Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation for viscous flow for binary mixtures of N-Methyl benzyl amine (NMBA) with 2-Methyl-2-butanol (2M2B), 2-Methyl-1-butanol (2M1B), and 3-Methyl-1-butanol (3M1B) were determined from measured densities (ρ), viscosities (η) and speeds of sound (u) at 303.15 K to 313.15 K. Influence Structural disparities on excess properties is discussed concerning intermolecular forces. The Prigogine – Flory – Patterson (PFP) theory identifies predominant molecular interactions, and the Jouyban – Acree model correlates density, speed of sound, and viscosity with composition. Thermodynamic activation parameters were calculated using the Eyring equation to study viscous flow thermodynamics. FT-IR and 1H NMR spectra of equimolar binary mixtures were analysed to confirm experimental findings through absorption bands (cm−1) and chemical shifts.

Thermo physical, spectroscopic and computational investigation of binary liquid mixtures at various temperatures and correlation with the Jouyban–Acree model (allyl alcohol, ethanoic acid, propanoic acid, and butanoic acid)

ABSTRACT The intermolecular interactions between allyl alcohol + short carboxylic acids (ethanoic acid, propanoic acid, and butanoic acid) binary liquid systems were studied both at the macro- and microscopic levels using a combined experimental and computational methodology. Thermo-physical properties of allyl alcohol and short carboxylic acids binary mixtures are studied at ambient atmospheric pressure over the entire composition range and at T= (303.15 K − 313.15 K). In the present study, the calculated excess/deviation properties are discussed in terms of molecular interactions of binary mixtures. The existence of the hydrogen bonding in the binary mixtures of allyl alcohol + short carboxylic acids were further confirmed by high level theoretical calculation, namely, the density functional theory (DFT-B3LYP) of 6–311++G (d,p) basis set was used to study the geometries, bond characteristics, interaction energies and of the hydrogen bonded complexes in gas phase were investigated via quantum chemical calculations

Thermo physical and spectroscopic properties of binary liquid mixtures at various temperatures and correlation with the Jouyban–Acree model (propargyl alcohol, ethanoic acid, propanoic acid and butanoic acid)

ABSTRACT A thorough investigation into binary mixtures of propargyl alcohol and various carboxylic acids (ethanoic, propanoic and butanoic) was conducted. Measurements of density (ρ), speed of sound (u) and viscosity (η) were meticulously performed across the entire range of mole fractions at temperatures (303.15 K−313.15 K) and atmospheric pressure (0.1 MPa). These data were used to calculate key thermodynamic and transport properties, including excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy of activation for viscous flow. The partial molar properties and infinite dilution molar partial properties were also determined for each binary system. Trends and behaviours were interpreted within the framework of intermolecular interactions, focusing on complex formation and specific chemical forces. The PFP theory and Jouyban–Acree model were critically applied, with confidence in the findings supported by FTIR studies.

Density-Gibbs energy correlation models for binary biofuel mixtures

The density of binary biofuel mixtures significantly influences fuel properties, directly affecting internal combustion engine performance. This research aims to develop correlational models to calculate densities in binary biofuel mixtures, leveraging the Gibbs energy mixing rule. Two correlation models are proposed: the ideal Gibbs energy mixing rule and the Gibbs energy quadratic mixing rule. These models aim to enhance the cross-interaction of Gibbs energy of activation (ΔG12) to improve predictive performance. Importantly, the constants of the existing models are directly related to thermodynamic parameters. To assess the accuracy of the models, observed densities were collected from four different binary systems: biodiesel + diesel, pure fatty acid ethyl ester + alcohol, biodiesel + alcohol, and alcohol binary mixtures, amounting to 2242 data points obtained from the literature. Based on mole fractions, both models were compared to earlier approaches. The examination revealed that the equation formulated by the quadratic mixing rule exhibited heightened precision and efficacy. Our data demonstrate that the extended ΔG12 provided the most accurate results.

Exploring relaxation behaviors in Hydrogen-Bond networks within binary mixtures of propylene carbonate and primary alcohols through broadband dielectric spectroscopy and molecular dynamic simulation

This work investigates the dielectric properties and the relaxation behaviors of propylene carbonate (PC) and its binary mixtures with methanol and ethanol. A coaxial-circular cutoff waveguide junction was employed to characterize broadband dielectric spectra ranging from 0.1 GHz to 18 GHz, and a two-group Debye model was used to extract relaxation parameters. Excess thermodynamic parameters, Kirkwood orientational correlation factors, and Bruggeman factors for PC-alcohol mixtures were also analyzed and presented. These data provide insights into microscopic dynamic processes as the PC concentration in the mixtures gradually increases. These processes include the continuous disassociation of the alcohols’ hydrogen-bond (H-bond) networks, the formation of new PC-alcohol H-bond networks, the parallel alignment of heterogeneous dipoles, and a significant enhancement of the dielectric effect. Furthermore, a series of molecular dynamics (MD) simulations using the TraPPE-UA forcefield were conducted, and the obtained thermodynamic and electromagnetic parameters demonstrated good agreement with experimental results. Based on radial distribution functions, dipole–dipole spatial orientational correlations, and H-bond life times extracted from the MD simulations, we observed the gradual formation of PC-cage and alcohol-cluster microstructures in PC-rich mixtures. The data and physical insights provided in this work are expected to have practical implications in high-energy battery applications and the pharmaceutical industry.

Solubility Determination, Solvent Effect, Thermodynamic Modeling, and Preferential Solvation of 2-Cyanoacetamide in Four Aqueous Binary Mixtures of Alcohols

Solubility Determination, Solvent Effect, Thermodynamic Modeling, and Preferential Solvation of 2-Cyanoacetamide in Four Aqueous Binary Mixtures of Alcohols

Study on the molecular interactions of some binary mixtures through thermodynamic properties and FT-IR spectra and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u) and viscosities (η) were measured for three binary mixtures of propargyl alcohol with tetra chloromethane, trichloromethane, and dichloromethane from 303.15 K to 313.15 K at atmospheric pressure across the composition range. Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation of viscous flow were calculated. Partial molar properties and infinite dilution molar partial properties were also determined for each system. Results suggest heteroassociates forming cross complexes and chemical forces with specific interactions. PFP theory was used to identify the predominant molecular interactions. The Jouyban–Acree model findings were discussed, considering mean relative deviation (MRDs) and individual relative deviation (IRD) between calculated and experimental data. FTIR studies were included to corroborate the experimental findings.

Environmental evaluation and comparison of hybrid separation methods based on distillation and pervaporation for dehydration of binary alcohol mixtures with life cycle, PESTLE, and multi-criteria decision analyses

To achieve net-zero CO2 emissions by 2050, improving energy efficiency in the chemical industry is crucial. The study focuses on an environmentally friendly hybrid distillation (D)-pervaporation (PV) process to enhance energy efficiency and purity in ethanol–water and isobutanol-water mixtures, these are typical wastes in the chemical industry. Three configurations—D + PV, D + PV + D, and D + PV + D with partial Heat Integration (HI)—are evaluated for separation of ethanol–water and isobutanol-water mixtures employing the Life Cycle Assessment with Environmental Footprint (EF) V3.1 (adapted) and ReCiPe 2016 Endpoint (H) V1.08 methods, using SimaPro V9.5 software and Ecoinvent V3.9.1 database. The study also incorporates a PESTLE analysis and Multi-Criteria Decision Analysis to identify the most advantageous process for ethanol and isobutanol scenarios. The research evaluates these systems in a comprehensive manner, including technology, CO2 emissions, impacts on human health, ecosystems, resources, and Total Annual Cost (TAC). The exploration of hybrid process enhancements includes alternative renewable energy sources (i.e., solar, wind, hydro, and biofuel) and comprehensive heat integration based on Pinch Analysis using Hint V2.2 software. Results indicate that D + PV + D is the most suitable for isobutanol-water scenarios based on MCDA and Pinch analysis. In isobutanol scenarios, D + PV + D + HI reduces CO2 emissions, and human health, ecosystems, and resources impact by 15.5 %, 11.2 %, 12.6 %, and 14.6 %, respectively, with a significant 40.0 % decrease in TAC compared to D + PV. Integrating renewable energy sources further enhances its sustainability, achieving a single score of approximately one-third lower than fossil fuel consumption. Promoting renewable energy and Integrating energy flows align seamlessly with Green Chemistry and Engineering principles, representing a crucial stride towards sustainable and eco-friendly industrial practices.

Thermo physical properties and IR spectral studies of some binary liquid mixtures and correlation with the Jouyban–Acree model

ABSTRACT Excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy for activation of viscous flow for binary mixtures of propargyl alcohol (J) with benzyl aldehyde (J1), benzylamine (J2) and benzyl alcohol (J3) components with selected compositions were determined from the measured values of densities (ρ), viscosities (η), and speeds of sound (u) of pure components and their mixtures from 303.15 K to 313.15 K. The effect of various functional groups on the excess properties has been discussed in terms of attractive forces between the components. The results of the Jouyban-Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion.FTIR studies have also been added to confirm the experimental findings of the investigated mixtures

Study on the molecular interactions of binary mixtures of allyl alcohol and amino-alcohol solvents through thermodynamic properties and FT-IR spectra and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of allyl alcohol with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol (aminomethyl propanol), and 1-amino propan-2-ol (isopropanol amine) were calculated at temperatures ranging from 303.15 to 313.15K and at atmospheric pressure over the entire composition range. Experimental measurements were used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and partialmolar properties at infinite dilution are also calculated. The Prigogine–Flory–Patterson (PFP) theory is applied to identify the predominant molecular interaction. The results of the Jouyban–Acree model are discussed in terms of the mean relative deviation (MRDs) and individual relative deviation (IRD) between the calculated and experimental parameters as an accuracy criterion. FTIR studies have also been added to confirm the experimental findings of the investigated mixtures.

Study on the molecular interactions of binary mixtures of allyl alcohol with isomeric amyl alcohol solvents through thermodynamic properties and FT-IR spectra and correlation with the Jouyban–Acree model

ABSTRACT Excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy for activation of viscous flow for binary mixtures of allyl alcohol (AA) with 2-methyl-2-butanol (2M2B), 2-methyl-1-butanol (2M1B) and 3-methyl-2-butanol (3M1B) components in different compositions were determined from the measured values of densities (ρ), viscosities (η) and speeds of sound (u) of pure components and their mixtures at various temperatures ranging from 303.15 K to 313.15 K. The excess properties have been discussed in terms of disruption of H-bonding and dipole–dipole interaction between the components of the mixtures. The Jouyban–Acree model results are discussed in terms of mean relative deviation (MRD) and individual relative deviation (IRD) between calculated and experimental parameters as an accuracy criterion and obtained a good agreement. The thermodynamic functions of activation of viscous flow have been estimated and tested. FTIR studies further confirm the experimental findings.

Thermophysical properties of binary liquid mixtures at various temperatures, supported by FTIR spectral studies and correlation with the Jouyban–Acree model (allyl alcohol, benzyl aldehyde, benzylamine and benzyl alcohol)

ABSTRACT Excess molar volume, excess isentropic compressibility, deviation in viscosity and excess Gibbs free energy for activation of viscous flow for binary mixtures of allyl alcohol (C) with benzyl aldehyde (C1), benzylamine (C2) and benzyl alcohol (C3) components in selected compositions were determined from the measured values of densities (ρ), viscosities (η) and speeds of sound (u) of pure components and their mixtures at 303.15–313.15 K. These results were analysed by different theoretical models, such as PFP and Jouyban–Acree model. The effect of various functional groups on the excess properties was discussed in terms of disruption of H-bonding and dipole–dipole interaction between the components of the mixtures. The thermodynamic results of the present investigation have been correlated with FTIR spectral studies and have obtained a good agreement.

FT-IR studies and excess thermodynamic properties of binary mixtures of propargyl alcohol and amino alcohols at different temperatures and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of propargyl alcohol with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol, and 1-amino propan-2-ol were calculated at temperatures ranging from 303.15 to 313.15 K and atmospheric pressure over the entire composition range. Experimental measurements are used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and infinite dilution molar partial properties are also calculated for each binary system. The Prigogine-Flory-Patterson theory is used to identify the most important interaction. The results of the Jouyban-Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion. FTIR studies have also been added to confirm the experimental findings of the investigated mixtures.

Neural Network Model of Surface Tension of Hydrocarbon–Alcohol Binary Mixtures

Since the correlation of surface tension of hydrocarbons and alcohol mixtures has great importance, this study is aimed to propose an artificial neural network model to correlate this thermodynamic property. To calculate the best network architecture and the optimal number of neurons, five sets of input variables and two transfer functions are examined. The results reveal that a feed-forward network with the structure of 5-14-1 and logsis and purelin as transfer functions for hidden and output layers, respectively, leads to the best accuracy. Moreover, it is revealed that choosing temperature, mole fraction, molecular weight of hydrocarbons, molecular weight of alcohols, and critical temperature as input variables can be efficient for an accurate correlation of the surface tension of selected chemicals. The results of the proposed artificial neural network model are also compared to the Shereshefsky and Langmuir thermodynamic models. The results obtained from 34 binary mixtures show the generality and acceptable accuracy of the proposed feed-forward network (with an average absolute relative deviation [AARD] of 0.36%) compared to the Shereshefsky (with an AARD of 0.37%, obtained for 31 binary mixtures) and Langmuir (with an AARD of 0.52%) thermodynamic models.

Thermophysical Studies on Binary Liquid Mixtures of Benzyl Alcohol and Alkylamines at 298.15–308.15 K

Thermophysical Studies on Binary Liquid Mixtures of Benzyl Alcohol and Alkylamines at 298.15–308.15 K

Thermodynamic Behavior of (2-Propanol + 1,8-Cineole) Mixtures: Isothermal Vapor-Liquid Equilibria, Densities, Enthalpies of Mixing, and Modeling.

Vapor pressures and other thermodynamic properties of liquids, such as density and enthalpy of mixtures, are the key parameters in chemical engineering for designing new process units, and are also essential for understanding the physical chemistry, macroscopic and molecular behavior of fluid systems. In this work, vapor pressures between 278.15 and 323.15 K, densities and enthalpies of mixtures between 288.15 and 318.15 K for the binary mixture (2-propanol + 1,8-cineole) have been measured. From the vapor pressure data, activity coefficients and excess Gibbs energies were calculated via the Barker's method and the Wilson equation. Excess molar volumes and excess molar enthalpies were also obtained from the density and calorimetric measurements. Thermodynamic consistency test between excess molar Gibbs energies and excess molar enthalpies has been carried out using the Gibbs-Helmholtz equation. Robinson-Mathias, and Peng-Robinson-Stryjek-Vera together with volume translation of Peneloux equations of state (EoS) are considered, as well as the statistical associating fluid theory that offers a molecular vision quite suitable for systems having highly non-spherical or associated molecules. Of these three models, the first two fit the experimental vapor pressure results quite adequately; in contrast, only the last one approaches the volumetric behavior of the system. A brief comparison of the thermodynamic excess molar functions for binary mixtures of short-chain alcohol + 1,8-cineole (cyclic ether), or +di-n-propylether (lineal ether) is also included.

Solid–liquid equilibria of binary mixtures of alcohols and aromatic hydrocarbons: experimental methods and modeling analysis

Solid–liquid equilibria of binary mixtures of alcohols and aromatic hydrocarbons: experimental methods and modeling analysis

Theoretical Two Dimensional Infrared Spectroscopy of Aqueous Solutions of tert-Butyl Alcohol: Variation of the Dynamics of Spectral Diffusion along the Percolation Transition.

Binary mixtures of water and tert-butyl alcohol (TBA) are known to exhibit the so-called percolation transition where small clusters of TBA molecules span into large aggregates beyond a threshold concentration of the alcohol. In the present study, we have investigated the linear and two-dimensional infrared spectral features of aqueous solutions of TBA for varying concentration of the alcohol along the percolation transition. The percolation transition is characterized through calculations of intermolecular radial distribution functions and average size of the largest cluster of TBA molecules. It is found that, with variation of alcohol concentration, the radial distribution functions of the central carbon atoms of TBA molecules show a nonmonotonic change in the height of the first peak and also the size of the largest cluster of TBA molecules show a jump in the increase of its size for TBA mole fraction between 0.04 and 0.06 corresponding to a transition from smaller clusters to larger spanning aggregates. However, it is found that the linear infrared spectrum of water does not exhibit any noticeable changes on variation of TBA concentration along the percolation transition. Subsequently, two-dimensional infrared (2DIR) spectra and vibrational frequency time correlation function of water are calculated for all the TBA-water solutions considered in this study. The spectral diffusion of water calculated from 2DIR is found to slow down with increase of the TBA concentration. The time scales of spectral diffusion of water, as characterized by the relaxation of frequency time correlation function, 2DIR metric of central line slope, and also the hydrogen bond time correlation functions, are found to exhibit a noticeable jump along the percolation transition. The hydrophilic group of TBA is found to retard the water dynamics more effectively than the hydrophobic groups. Also, the jump in the dynamical slowdown along the percolation transition is found to be more significant for water molecules at the hydrophilic sites.

Densities, Viscosities, and Derived Properties for Binary Mixtures of Long-Chain Alcohols of 1-Hexanol + 1-Pentanol, + 2-Pentanol, + 2-Methyl-1-butanol, + 1-Heptanol, and + 1-Octanol from 288.15 to 338.15 K

Densities and viscosities for binary mixtures of long-chain alcohols are important to design transfer heat and mass equipment and to interpret the kind of interactions that occur in the studied blends. Current investigation indicated the measurements of densities and viscosities for liquid mixtures of 1-hexanol + 1-pentanol, + 2-pentanol, + 2-methyl-1-butanol, + 1-heptanol, and + 1-octanol from 288.15 to 338.15 K at atmospheric pressure and over the whole range of mole fractions. A vibrating tube densimeter and a glass capillary viscometer were used to measure the density and viscosity of the alcohol binary mixtures, respectively. Experimental measurements of the pure alcohols have been compared with the data reported in the literature using average absolute percentage deviation (AAPD) as a criterion. The obtained results demonstrated for density an AAPD of 0.023% and for viscosity an AAPD of 0.597%, which is a good agreement between the experimental findings and literature data. Excess molar volume and viscosity deviation present negative deviations for all the alcohol mixtures at the conditions considered in this research. These results indicate that the mixture suffers a volume contraction, which is caused by intermolecular forces of attraction between different alcohol molecules. The Redlich–Kister equation is used to fit the excess molar volume and viscosity deviation. Kinematic viscosities of the binary blends have been calculated through the Nava-Ríos et al. and McAllister equations.

Complex formation and microheterogeneity in water–alcohol binary mixtures investigated by solvatochromic study

Complex formation and microheterogeneity in water–alcohol binary mixtures investigated by solvatochromic study