Ultrasonic and infrared study of molecular interactions in ternary mixtures of 1-naphthol and 2-naphthol with 2-propanone in benzene

The measurements of ultrasonic velocity and density were made for the ternary mixtures of l-naphthol/2-naphthol with 2-propanone in benzene at 20, 30 and 40°C in the mole fraction range of 0.00 to 0.05. Adiabatic compressibility and intermolecular free length have been evaluated using ultrasonic velocity data. The non-linear variation of ultrasonic velocity and allied parameters with mole fraction indicates solute-solute interactions through hydrogen bonding between unlike molecules. Results of ultrasonic velocity and density measurements are further supported by FT-IR spectra. The change in transmittance as well as the shift in the frequency of the representative peak of the OH stretching in FT-IR spectra give inferences about the complex formation.     

Molecular interaction and other thermodynamic properties in ternary liquid mixtures

Molecular interaction, adiabatic compressibility, intermolecular free length, molar volume, available volume and free volume have been computed by measuring ultrasonic velocity and density at 23°C in three ternary liquid mixtures with p-xylene as common component. The systems are I p-xylene-acetone-carbon tetrachloride, II p-xylene-acetone-cyclohexane and III p-xylene-benzene-cyclohexane. Molecular interaction is maximum when the mole fraction of acetone is 0.5 in I and 0.6 in II. It remains almost constant in III indicating no interaction in this case. The excess properties have also been given and the interactions explained.     

Ultrasonic study of nitric acid

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Study of intermolecular interactions in binary mixtures of 2′-chloro-4-methoxy-3-nitro benzil in various solvents and at different concentrations by the measurement of acoustic properties

Density (ρ), ultrasonic velocity (u), adiabatic compressibility (β), apparent molar volume (Ø), acoustic impedance (Z), intermolecular free length (L_f), relative association (RA) of binary mixtures of 2′-chloro-4-methoxy-3-nitro benzil (abbreviated as 2CBe) in ethanol, acetonitrile, chloroform, dioxane and benzene were measured at different concentrations at 298 K. Several useful parameters such as excess density, excess ultrasonic velocity, excess adiabatic compressibility, excess apparent molar volume, excess acoustic impedance and excess intermolecular free length have been calculated. These parameters are used to explain the nature of intermolecular interactions taking place in the binary mixture. The above study is useful in understanding the solute – solvent interactions occurring in different concentrations at room temperature.     

Ultrasonic velocity, density, viscosity and their excess parameters of the binary mixtures of tetrahydrofuran with methanol and o-cresol at varying temperatures

The ultrasonic velocity, density and viscosity of binary mixtures of tetrahydrofuran (THF) with methanol and o-cresol were measured at 293, 303 and 313 K over the entire range of composition. Using these experimental data, various thermo-acoustic parameters such as deviation in isentropic compressibility Δκ_s, excess molar volume , viscosity deviation Δη and excess Gibb’s free energy of activation for viscous flow ΔG^∗E have been calculated and fitted to Redlich-Kister polynomial equation. The deviation/excess parameter were plotted against the mole fraction of THF over the whole composition range. The observed negative and positive values of deviation/excess thermo-acoustic parameters were explained on the basis of the intermolecular interactions present in these mixtures. Since methanol is less acidic than o-cresol, the removal of proton from methanol is less likely than the removal of proton from o-cresol which is more acidic than methanol. Hence the intermolecular interaction in the mixture of THF with o-cresol is found to be stronger than mixture of THF with methanol, which is reflected from the observed positive and negative values of excess thermo-acoustic parameters. Thus it may be concluded that THF + o-cresol mixture exhibits strong intermolecular interaction. However, dispersive forces are responsible for THF + methanol mixture due to weak interaction. Further, Nomoto, Junjie, CFT and Flory’s theory were applied for evaluating the ultrasonic velocity theoretically. The theoretical evaluation of ultrasonic velocity based on molecular models in liquid mixtures has been used to correlate with the experimental findings and to know the thermodynamics of the mixtures. The comparison of theoretical and experimental results provides better understanding about the validity of the various thermodynamic, empirical, semi empirical and statistical theories.     

Ultrasonic studies of intermolecular interactions in binary mixtures of 4-methoxy benzoin with various solvents: Excess molar functions of ultrasonic parameters at different concentrations and in different solvents

Density (ρ), ultrasonic velocity (U), for the binary mixtures of 4-methoxy benzoin (4MB) with ethanol, chloroform, acetonitrile, benzene, and di-oxane were measured at 298 K. The solute–solvent interactions and the effect of the polarity of the solvent on the type of intermolecular interactions are discussed here. From the above data, adiabatic compressibility (β), intermolecular free length (L_f), acoustic impedance (Z), apparent molar volume (Ø), relative association (RA) have been calculated. Other useful parameters such as excess density, excess velocity and excess adiabatic compressibility have also been calculated. These parameters were used to study the nature and extent of intermolecular interactions between component molecules in the binary mixtures.     

Studies on intermolecular interaction on binary mixtures of methyl orange-water system: excess molar functions of ultrasonic parameters at different concentrations and at different temperatures

Density (ρ), viscosity (η) and ultrasonic velocity (u) of binary mixtures of methyl orange and water were measured at different concentrations and at different temperatures; several useful parameters such as excess volume, excess velocity, and excess adiabatic compressibility have been calculated. These parameters are used to explain the nature of intermolecular interactions taking place in the binary mixture. The above study is helpful in understanding the dye/solvent interaction at different concentration and temperatures.     

Estimating organic chain length through sound velocity measurements

The ability to measure the length of polymers while monitoring their production is evidently extremely valuable, but is also a useful tool for chemical identification purposes at other times, e.g. the analysis of waste water. A study of the relationship between velocity of sound and chain length has been carried out. Initial studies were performed on two model systems; a series of pure liquid n-alkanes (pentane to hexadecane) and 1-alcohols (methanol to 1-dodecanol). This study was extended to look at an industrially significant system of dimethylsiloxanes 200 fluid (L2, 0.65 cSt) to 200 fluid (5000 cSt). Corresponding density data have been taken from the literature and the adiabatic compressibility determined. The measured adiabatic compressibility has been compared with two molecular models of wound velocity, the Schaaffs model and a development of the Urick equation. The Urick equation approach is based on a determination of the compressibility of the methylene or siloxane repeat units which make up the chains in these linear molecules. We show that the Urick equation approach accurately predicts sound velocity and compressibility for the higher members of each series, whilst the Schaaffs approach fails for the 1-alcohols. We suggest that this is because of the influence of the hydroxyl end group through hydrogen bonding with methylene groups within the chain. This interaction modifies the derived compressibility of the methylene groups, so reducing their compressibility relative to that of the n-alkanes. The technique described provides valuable new insights into end-group, intermolecular and intra-molecular interactions in liquid linear-chain molecules. From this detailed analysis of the mechanisms involved, a model is derived. This model can give very precise estimations of the composition of a pure liquid. In the case of mixtures of polymers, it is necessary to use the modified Urick equation and then, in addition, the concentration dependence of both the velocity of sound and the density must be measured.     

Ultrasonic and optical studies on charge transfer complexes of p-chloranil with certain aromatic hydrocarbons in DMSO at 303.15 K

Ultrasonic investigation has been carried out on six ternary systems to establish the complex formation between p-chloranil (acceptor) and six aromatic hydrocarbons (donors), namely, benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene in DMSO medium at 303.15 K and at atmospheric pressure. Studies were carried out in the concentration range of 0.002 to 0.02 M of acceptor and donor with equimolar concentration of the two components in solution. The trend in the acoustical parameters and magnitude of excess thermo acoustical parameters has been used to identify the existence of strong intermolecular interaction through charge transfer complex formation. The formation of 1:1 complex was also confirmed by UV-Visible spectroscopic method at 303.15 K in these systems. It may be pointed out that the formation constants of the charge transfer complexes determined by Benesi-Hildebrand (spectroscopic) and Kannappan (ultrasonic) methods show similar trend and well establish the influence of structural aspect of the donor aromatic compounds on the stability of charge transfer complexes.     

Ultrasonic and spectroscopic studies on hydrogen bonded complexes of aromatic amine and aryl ketones in n-hexane at 303.15 K

Viscometric and ultrasonic studies have been carried out in n-hexane solutions, containing equimolar concentration from 0.02 to 0.2 M of aromatic ketones and N-methylaniline (NMANI), at 303.15 K and at atmospheric pressure. The ketones studied in the present investigation are acetophenone (ACP), 4-chloroacetophenone (ClACP) and 4-methylacetophenone (MACP). The behaviour of measured ultrasonic velocity (u), density (ρ) and viscosity (η) and also the computed acoustic parameters provide strong evidence for the presence of strong solute-solute interactions in the three ternary systems. Excess molar volume and excess thermo acoustic parameters reveal the existence of hydrogen bonded complexes between the solute molecules, ketones and secondary amine. The variation of these parameters with the concentration shows that the existing interactions are influenced by the structure of components and functional groups of the components involved. An attempt has been made to confirm the formation of 1:1 complexes in these systems through UV-visible spectroscopic method at 303.15 K. The calculated values of formation constants of the charge transfer complexes both by acoustic and optical methods agree satisfactorily. The variation in the values of formation constant reveals that electron releasing substituent in the acetophenone molecule enhances the stability while electronegative substituent decreases the stability of the complex. The negative values of free energy of formation of these three complexes indicate that these complexes are thermodynamically stable.     

Kinetics and product distribution of p‐nitrophenyl phosphate dianion solvolysis in ternary DMSO/alcohol/water mixtures are compatible with metaphosphate formation

The rate of solvolysis of p‐nitrophenyl phosphate (PNPP) dianion in DMSO/water strongly decreases by increasing water concentration. Addition of linear alcohols (methanol, propanol, butanol, pentanol, and hexanol) at constant DMSO/water molar ratio produced an even sharper rate decrease. Alkyl phosphate formation, resulting from PNPP solvolysis in ternary DMSO/water/alcohol mixtures, increased with alcohol concentration and was essentially temperature independent. Methanol and hexanol were the poorest nucleophiles under all conditions. Activation energies and enthalpies for solvolysis in ternary mixtures were similar and entropies varied with alcohol concentration. Taken together these results can be best interpreted in terms of a dissociative mechanism with the intervention of metaphosphate. Copyright © 2011 John Wiley & Sons, Ltd.     

位阻效应对受阻酚杂化体系阻尼机理的影响

针对尚未解决的受阻酚结构变化与杂化体系阻尼机理间关系的问题,本文采用分子动力学模拟方法构建了三种受阻程度不同的受阻酚/聚合物杂化体系,从理论上探讨了位阻效应对阻尼机理的影响.对体系氢键相互作用、结合能、相对自由体积及扩散系数进行模拟分析表明,位阻效应对受阻酚分子内氢键相互作用有显著的弱化效果,可减少小分子团聚倾向,有利于小分子与聚合物分子间氢键相互作用的形成.但是,过高的位阻对小分子运动有阻碍作用,不利于小分子与聚合物形成强烈的氢键键合,也即不利于杂化体系阻尼性能的提高.因此,如何选择受阻程度适中的受阻酚是制备高阻尼杂化材料的一关键要素.     

Phase diagram involving the mesomorphic behavior of binary mixture of sodium oleate and orthophosphoric acid

The present investigation deals with the binary mixture of two non-mesogenic compounds, viz. sodium oleate (Naol) and orthophosphoric acid (H₃PO₄) which exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixtures with concentrations ranging from 10% to 90% Naol in H₃PO₄ exhibit SmA, SmC, SmE and SmB phases, sequentially when the specimen is cooled from its isotropic phase. Physical properties, such as ultrasonic velocity, adiabatic compressibility and molar compressibility, show anomalous behavior at the isotropic to mesosphase transition.     

Volumetric, viscometric, acoustical, and optical studies of glutamic acid in aqueous zinc and copper chloride solutions

Ultrasonic velocity, density, viscosity and refractive index measurements of L-glutamic acid in aqueous zinc chloride and copper chloride solutions have been carried out at 303.15K. From these experimental data isentropic compressibility, acoustic impendence, relative association, free path length, apparent molar volume, apparent molar isentropic compressibility and molar refraction of L-glutamic acid in aqueous solutions of electrolytes are evaluated. These values have been used to explain molecular association, solutesolvent interaction through hydrogen bonding and solvation. Viscosity data have been analyzed in the light of Jones-Dole equation and the constants A and B have been estimated and interpreted in terms of ion-ion, ionsolvent and molecular interactions occurring in solutions.     

Phase transition studies in N(p-n-pentyloxy benzylidene) p-n-decyl aniline

The temperature dependences of the molar volume, the ultrasonic velocity and the refractive index in N(p-n-pentyloxy benzylidene) p-n-decyl aniline, which exhibits nematic, smectic-A and smectic-B, phases, are presented. The isotropic-nematic and smectic-A-smectic-B phase transitions are found to be of first order while the nematic-smectic-A transition is of second order. The thermal expansion coefficient (a) computed from the molar volume data agrees with a second-order N-S_A transition. The computed adiabatic compressibility β_ad, molar sound velocity (or Rao number R_n ) and molar compressibility (or Wada constant A) are presented.     

Study of acoustic parameters of binary mixtures of a nonpolar liquid with polar liquid at different frequencies

The densities (ρ) and ultrasonic velocities (C) of binary mixture of diisopropyl ether (DIPE) and bromobenzene (BB) have been measured at different frequencies (1 MHz, 3 MHz and 5 MHz) over the entire range of mole fraction of diisopropyl ether (DIPE) at temperature 303 K. The intermolecular free length (L _f ), isentropic compressibility (β), acoustic impedance (Z) and excess values of isentropic compressibility (β ^E ) and acoustic impedance (Z^E) have been computed using values of ultrasonic velocity (C) and density (ρ). The ultrasonic velocity, intermolecular free length are positive whereas the excess values of isentropic compressibility and acoustic impedance are negative over the entire composition range of DIPE which indicates presence of specific interactions between unlike molecules. The results are discussed in the light of intermolecular interactions occurring in the mixtures.      

Effect of frequency on acoustic parameters in a binary mixture of polar liquids

The densities (α) and ultrasonic velocities (C) of binary mixtures of a polar liquid like acetone and toluene have been measured at different frequencies (lMHz, 3MHz and 5MHz) over the entire range of mole fraction of acetone at temperature 303.16k. The intermolecular free length (L _f ), isentropic compressibility (β), acoustic impedance (Z), excess values of isentropic compressibility (β ^E ) and acoustic impedance (Z ^E ) have been computed using values of ultrasonic velocity (C) and density (α). The ultrasonic velocity (C), intermolecular free length (L _f ) and excess values of isentropic compressibility are positive whereas excess values of acoustic impedance is negative for the entire composition range which indicates the specific interaction between unlike molecules. The results are discussed in the light of intermolecular interactions occurring in the solutions.     

运用液体声学理论研究超临界二氧化碳的声特性

利用液体声学模型，根据美国国家标准局提供的二氧化碳声速、密度、摩尔体积和绝热压缩系数数据，计算了气态、液态和超临界态二氧化碳在不同温度和压力条件下的摩尔声速、摩尔压缩系数及Van der Waals 常数. 分析发现，在较宽的温度和压力范围内，液体中的声学模型能够很好地运用于超临界态二氧化碳的研究. 并在液体声学模型适用范围内，计算了超临界二氧化碳在不同温度及压力状态下的表面张力、粘度、自扩散系数，为超临界流体技术提供了参考数据，并分析了这些参量的变化规律.     

Chromonic liquid crystalline phase transition involving a biphasic region of nematic and hexagonal phases

We report the results of our studies on the optical and thermal properties of binary mixture of two compounds viz. abietic acid and poly ethylene glycol (PEG). The mixture shows a very interesting co-existent biphasic region of lyotropic nematic (N + I) and intermediate hexagonal (M + I) phases, sequentially when the specimen is cooled from its isotropic phase at different concentrations of abietic acid in PEG. The aggregated molecular size has been confirmed by X-ray studies. The temperature variation of optical anisotropy, electrical conductivity, ultrasonic velocity, and molar and adiabatic compressibility has also been discussed.     

Phase transition studies in polymesomorphic compounds (ii): Ultrasonic velocity studies in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline

The variation of ultrasonic velocity in N-(p-n-hexyloxy benzylidene) p-n-butyl aniline with temperature in the isotropic, nematic, S_A S_B and S_G phases is measured. All the phase transitions are of first order. The adiabatic compressibility β _ad , molar sound veclocity or Rao number R_n , and molar compressibility or Wada constant A are computed. Molar sound velocity and molar compressibility of HBBA are compared with the values of other compounds. They are found to be in good agreement with theory.