X-Ray Studies of 2-Methyl-2-Propanol Solution in Cyclohexane

Abstract

Changes in the mean least intermolecular distances in a solution of 2-methyl-2-propanol in cyclohexane with increasing concentration of the former were found to be non-linear. Both in the range of low (0.005–0.04 molar fraction) and high (0.45–0.75 molar fraction) concentrations of the solutions studied local maxima of the mean least intermolecular distance were observed. In the range from 0.8 to 1 molar fraction the value of this parameter remained constant. Results obtained in this work prove the absence of the specific structural properties of a low concentration alcohol solution observed in other solvents. The occurrence of the local maxima proves that cyclohexane is a non-active solvent. Owing to this the molecules of the solute and the solvent assume positions ensuring homogeneity of the solvents.     

Density and Volume Properties of the 2-Methoxyethanol + 1,2-Dimethoxyethane + Water Ternary Solvent System at Various Temperatures

Abstract

Densities (ρ) of the ternary mixtures 2-methoxyethanol +1,2-dimethoxyethane + water have been measured at 19 temperatures in the range - 263.15 ≤ T/K ≤ 353.15. The experimental data were processed by empirical relations accounting for the dependence of ρ on temperature and ternary composition expressed as mole fraction of the components (0≤x_i ≤1). All checked equations seem to be suitable for correlation purposes, in order to obtain interpolated values in correspondence to experimental data gaps. Furthermore, the excess molar volume (V^E ) has been investigated to make evident the possibility of forming stable solvent-cosolvent adducts. The excess property has been interpreted on the basis of specific intermolecular interactions between the components.     

Densities, Viscosities, and Excess Gibbs Energy of Activation for Viscous Flow, for Binary Mixtures of Dimethyl Phthalate (DMP) with 1-Pentanol, 1-Butanol, and 1-Propanol at Two Temperatures

Summary. Density (ρ) and viscosity (η) values of the binary mixtures of DMP + 1-pentanol, 1-butanol, and 1-propanol over the entire range of mole fraction at 298.15 and 303.15 K were measured in atmospheric pressure. The excess molar volume (V ^E), viscosity deviations (Δη), and excess Gibbs energy of activation for viscous flow (G^*E) were calculated from the experimental measurements. These results were fitted to Redlich–Kister polynomial equation to estimate the binary interaction parameters. The viscosity data were correlated with equations of McAllister. The calculated functions have been used to explain the intermolecular interaction between the mixing components.     

Viscosity of Aqueous Solutions of n-butylamine,sec-butylamine and tert-butylamine

Abstract

Viscosities of the systems, water (W) + n-butylamine (NBA), W + sec-butylamine (SBA) and W + tert-butylamine (TBA) have been measured in the temperature range 298.15–323.15K. The viscosities (η) and excess viscosities (η^E) have been plotted against mole fraction of amines (X ₂). On addition of amines to water, viscosities first increase rapidly, then pass through maxima at 0.2 mole fraction of amines and then decline continuously as the addition of amines is continued. η^E show large positive values, with maxima also at 0.2 mole fraction of amines. The maxima of the curves of η and η^E vs. mole fraction of butylamines follow the order, W + TBA > W + SBA > W + NBA. The ascending part of the η vs. X ₂ curves in the water-rich region is explained by the hydrophobic hydration caused by the hydrocarbon tails and the hydrophilic effect due to — NH₂ group of amines. Following the maxima, amine - amine association is preferred, which accounts for the steady decrease of viscosity up to the pure state of amines.     

X-Ray Diffraction Study of Some Liquid Naphthalene Derivatives

Abstract

The structure of the liquids 1-Methylnaphthalene C₁₀H₇—CH₃ and 1-Chloronaphthalene C₁₀H₇—Cl was investigated using X-ray diffraction at 293 K. Monochromatic radiation MoK_α (λ = 0.7107Å) enabled determination of the scattered radiation inteasity between S₀ = 4\pi sin υ₀/λ = 0.430 Å^?1 and S _max = 14.311 Å-1. Angular distributions of X-ray scattered intensity were measured, and differential radial distribution functions of electron density (DRDFs) were calculated. The mean distances between the neighbouring molecules and the ranges of the spheres of intermolecular ordering were found. X-ray structural analysis was applied for determination of the packing coefficient of molecules of the liquids studied. A simple model of short-range arrangement of the molecules was proposed, which seems to be valid for other weakly polar monosubstituted naphthalene derivatives in the liquid phase.     

H-NMR Spectral and Dielectric Behaviours of the 2-Metoxyethanol-Tetrahydrofuran Solvent System

Abstract

Relative permittivities (E ₁₂) have been measured for 2-metoxyethanol (ME)-tetrahydrofuran (THF) binary liquid mixtures over the whole compositions range at various temperatures ranging from 291.15 K to 308.15 K. The experimental data were used to test some empirical equations of the type: y ₁₂ = y ₁₂(t) and y ₁₂ = y ₁₂ (X ₁) [where: y ₁₂-E ₁₂]. From all these data, the temperature coefficients of relative permittivities (α₁₂) and the excess extrathermodynamic parameters ε^E were calculated. The ¹H-NMR spectra of liquid binary mixtures of ME and THF, were recorded at 298 K over almost the whole range of the mixed solvent compositions. From these data the values of the values of the spectral structural parameters were found, δδ(ME-THF). These structural parameters as a function concentration suggest the formation of stable 3ME.THF types intermolecular complexes.     

Thermodynamics of interaction of L-α-phenylalanine with urea and dimethylformamide in aqueous solution

The thermal effects of solution of L-phenylalanine in aqueous solutions of urea and dimethylformamide (DMF) at 25°C were determined. The solubility of L-phenylalanine in water and aqueous DMF solutions was measured. The standard enthalpies, free energies, and entropies of solution of the amino acid in aqueous solutions of amides were calculated. The parameters of pair and ternary amino acid-amide interactions were determined within the framework of the McMillan-Mayer theory. The amino acid-amide pair interaction is accompanied by a decrease in the Gibbs free energy, controlled by the entropy term with DMF and by the enthalpy term with urea. The interaction of L-phenylalanine with two amide molecules is repulsive, which in the case of DMF leads to an increase in the standard free energies of solution of the amino acid at the amide mole fraction X ₂ > 0.05.     

Acoustical study on ternary mixture of dimethyl acetamide (DMAC) in diethyl ether and isobutyl methyl ketone at different frequencies

The experimental density (ρ) and the velocity (U) for ternary mixture of dimethyl acetamide diethyl ether and isobutyl methyl ketone at different frequencies (2, 4, 6 and 8 MH_Z) have been measured at a constant temperature of 308 K. These data have been used to compute acoustic impedance (Z), adiabatic compressibility (K _s), intermolecular free length (L_f ), molar volume (V_m ), molar sound velocity (R), molar compressibility (B), available volume (V _a), Lennard-Jones potential repulsive term exponent (n), relative association (R _A), interaction parameter (X) and excess values of some of the above parameters for entire range of mole fraction and are interpreted to explain molecular interaction occurring in the liquid mixture.     

Excess Volumes of Ternary Mixtures Containing N-Methylcyclohexylamine,Benzene with 1-Alkanols at 303.15 K

Abstract

New excess volume data have been measured for three ternary mixtures at 303.15 K. The mixtures included N-methylcyclohexylamine and benzene as common components. 1-propanol, 1-butanol and 1-pentanol were chosen as non-common components. The data were compared with those predicted by empirical relations. The experimental results have been analysed in terms of intermolecular interactions between unlike molecules.     

Heterogeneity in binary mixtures of (water + tertiary butanol): temperature dependence across mixture composition

The temperature dependence of solution heterogeneity in binary mixtures of water and tertiary butanol (TBA) and its effects on a chemical reaction have been investigated by using steady-state and time-resolved spectroscopic experiments within the temperature range of 278 ≤ T/K ≤ 373. Eleven different mole fractions of TBA, covering extremely low TBA mole fractions to pure TBA, have been considered. An organic chromophore that undergoes a photoexcited intramolecular charge-transfer reaction is employed to reveal the signature of the solution heterogeneity. Upon increasing the solution temperature, the absorption spectrum of the dissolved chromophore exhibits a red shift at very low TBA concentrations but shifts toward higher energy (blue shift) at higher alcohol concentrations. This is a reflection of temperature-assisted aggregation of TBA molecules in very dilute aqueous solutions. The magnitude of the temperature-induced red shift is the largest at around 0.04 mol fraction of TBA, and a larger variation of the spectral line width across the temperature suggests enhanced solution heterogeneity. Reaction time constants measured at various mixture compositions are found to follow an Arrhenius-type temperature dependence. The average activation energy, when plotted as a function of mixture composition, steeply rises with TBA concentration in the limit of the very low TBA mole fraction and then suddenly levels off to a plateau upon further addition of TBA. The alcohol concentration-dependent activation energy abruptly changes its slope at a TBA mole fraction ～0.1, at which a transition from the three-dimensional water-type network to the zigzag alcohol chain structure is known to occur. The plateau value of the activation energy is ～6k(B)T and agrees well with the earlier estimate for the same chromophore from the pure solvent data at room temperature. The observed increase in the spectral red shift with temperature at low TBA mole fractions is in general agreement with the existing experimental results which support the view that temperature assists the aggregation of TBA molecules in dilute aqueous solutions of TBA. However, unlike in the small-angle neutron scattering study [ Bowron, D. T.; Finney, J. L. J. Phys. Chem. B 2007, 111, 9838], which finds clustering of TBA molecules reaching a maximum at ～353 K, the present data do not indicate any such temperature maximum within the temperature range of 278 ≤ T/K ≤ 373.     

Stabilization of a high energy molecular conformation by specific intermolecular forces, a novel planar benzylideneaniline system

The system containing six benzylideneanilines (BA) has been studied: Group 1:

Thermodynamic and acoustic properties of binary mixtures of PEGDME 250 with 1-propanol and 1-butanol at 293, 303 and 313°K

ABSTRACT

The work presented in this paper deals with the study of thermodynamic properties of new working fluids for absorption machines, mainly for characterisation of absorbent–refrigerant pairs that could improve the cycle performance. The study of atomic motion in liquids plays an important role in understanding the solid-like behaviour of liquids. The accurate measurement of the energy changes due to scattering can be used to study the dynamical behaviour of liquids. Measurements of the ultrasonic velocity (u), density (ρ) and viscosity (η) for binary mixtures of polyethylene glycol 250 dimethyl ether with 1-propanol and 1-butanol have been made at three temperatures (T = 293, 303 and 313 K) over the entire composition range in order to investigate the nature of intermolecular interactions between the components of these liquid mixtures. Non-linear variation of derived quantities with the mole fraction supports the molecular interaction occurring between component molecules.     

H/D isotope effect on charge‐inverted hydrogen‐bonded systems: Systematic classification of three different types in H3XH…YH3 (X = C,Si, or Ge,and Y = B,Al, or Ga) with multicomponent calculation

Three different H/D isotope effect in nine H₃XH(D)^…YH₃ (X = C, Si, or Ge, and Y = B, Al, or Ga) hydrogen‐bonded (HB) systems are classified using MP2 level of multicomponent molecular orbital method, which can take account of the nuclear quantum nature of proton and deuteron. First, in the case of H₃CH(D)^…YH₃ (Y = B, Al, or Ge) HB systems, the deuterium (D) substitution induces the usual H/D geometrical isotope effect such as the contraction of covalent R(C? H(D)) bonds and the elongation of intermolecular R(H(D)^…Y) and R(C^…Y) distances. Second, in the case of H₃XH(D)^…YH₃ (X = Si or Ge, and Y = Al or Ge) HB systems, where H atom is negatively charged called as charge‐inverted hydrogen‐bonded (CIHB) systems, the D substitution leads to the contraction of intermolecular R(H(D)^…Y) and R(X^…Y) distances. Finally, in the case of H₃XH(D)^…BH₃ (X = Si or Ge) HB systems, these intermolecular R(H(D)^…Y) and R(X^…Y) distances also contract with the D substitution, in which the origin of the contraction is not the same as that in CIHB systems. The H/D isotope effect on interaction energies and spatial distribution of nuclear wavefunctions are also analyzed. © 2015 Wiley Periodicals, Inc.     

Thermodynamics of transfer of sodium chloride from water to aqueous sucrose at 25°C

Enthalpies of transfer of sodium chloride over the mixed-solvent range from pure water to mole fraction sucroseX ₃=0.05 (50 wt. %) were determined calorimetrically at 25°C. These were combined with free energies of transfer at constant molality (per 100 g of mixed solvent) calculated from isopiestic activity coefficients to yield negative entropies of transfer. The positive free energy is approximately a linear function ofX ₃, and the negative enthalpies show that the free energies and activity coefficients of NaCl increase with temperature. The enthalpy behavior of NaCl in aqueous hydrogen peroxide and the urea is very similar to that in the present study, indicating the possibility of rough colligative effect for such systems.     

Determination of Monomer Unit Sequence Distribution and Linkage Configuration of Copolymers of Styrene and Citraconic Anhydride,and Possibility of a Participation of Electron Donor-Acceptor Complex in the Copolymerization

Abstract

The copolymerization system of styrene (ST) and citraconic (α-methymaleic) anhydride (CA) was found to form semi-alternating copolymers when polymerized with a total monomer concentration of 4 mol/L in CCl₄ at 50°C, with alternating copolymers being formed only when the CA mole fraction in feed was greater than 0.9. More than 50% of the linkage configurations at the cyclic CA units in the copolymers were found to be in cis configuration. This, together with the following observations, is consistent with a participation of the electron donor-acceptor (EDA) complex formed between ST and CA: (a) the complex participation model fits best, although only marginally, to the experimental triad mole fraction of alternating sequences; (b) the alternating monomer unit sequences and the cis linkage configuration at the cyclic CA units are more efficiently formed in non polar CCl₄ solutions than in polar methy ethyl ketone. The equilibrium constant for the EDA complexation of ST and CA in CCl₄ at 23°C is determined to be 0.142 ± 0.015 L/mol.     

Experimental and ab initio structural study of the ketotin compounds,X3SnCR2CH2COMe: crystal structures of X3SnCMe2CH2COMe (X = Cl and I)

The MeCOCH₂CMe₂ ligand in X₃SnCMe₂CH₂COMe ( 2 ; X = halide) acts as a C,O‐chelating group both in the solid state and in non‐coordinating solutions. The intramolecular Sn? O bond lengths in trigonal bipyramidal 2 (X = Cl and I), as determined by X‐ray crystallography, indicate that the stronger interaction occurs in 2 X = Cl. Comparisons with the Sn? O bond lengths in the estertin trihalides, X₃SnCH₂CH₂CO₂R ( 1 ; R = Me), suggest that the latter form stronger chelates than do 2 . In chlorocarbon solution, 2 (X = Cl, I) undergoes exchange reactions, as shown by NMR spectra, to give all possible halide derivatives, ∑(Cl_nI_3?nSnCMe₂CH₂COMe) (n = 0–3). Various ab initio calculations on 2 and X₃SnCH₂CH₂COMe ( 3 ) have been carried out. Comparisons of the theoretical and experimental structures of 2 for X = Cl or I are reported. Copyright © 2005 John Wiley & Sons, Ltd.     

Excess Volumes of Binary Mixtures of Benzene + 1-Alkanols at 303.15 K

Abstract

Excess molar volumes V^E of binary mixtures of benzene + 1-propanol, + 1-butanol, + 1-pentanol, + 1-hexanol, + 1-heptanol, + 1-octanol, + 1-nonanol and 1-decanol were measured at 303.15 K. The V^E values are positive over the entire range of composition for these mixtures. The results are discussed in terms of intermolecular interactions.     

Röntgenographische und schwingungsspektroskopische Untersuchung der Mischkristallreihen Cu3MxM′;1-xX4 (M,M′ = V,Nb, Ta; X = S,Se) mit Sulvanitstruktur

X-ray and Vibrational Spectroscopical Investigation of the Mixed Crystal Series Cu₃M_xM′_1-xX₄ (M, M′ = V, Nb, Ta; X = S, Se) with Sulvanite Structure Solid solutions Cu₃M_xM′_1-xX₄ (M, M′ = V, Nb, Ta; X = S, Se) with Sulvanite structure have been prepared in the range 0 ≤ x ≤ 1 by solid state reaction between 600°C and 900°C. The lattice constants decrease linearly with x. The UR active antisymmetrical as well as the Raman active symmetrical M–X stretching vibrations may be attached to independently vibrating MX₄ and M′X₄ tetrahedrons.     

Intermolecular bond lengths: extrapolation to the basis set limit on uncorrected and BSSE‐corrected potential energy hypersurfaces

Geometry optimizations were carried out for the (HF)₂, (H₂O)₂, and HF–H₂O intermolecular complexes using the MP2/aug‐cc‐pVXZ {X=2, 3, 4, and 5} theoretical models on both the uncorrected and counterpoise (CP) corrected potential energy hypersurfaces (PES). Our results and the available literature data clearly show that extrapolation of intermolecular distances to the complete basis set (CBS) limit is satisfactory on PESs corrected for BSSE. On the other hand, one should avoid such extrapolations using data obtained from uncorrected PESs. Also, fixing intramolecular parameters at their experimental values could cause difficulties during the extrapolation. As the available literature data and our results clearly show, the MP2/aug‐cc‐pVXZ {X=2, 3, 4} data series of intermolecular distances obtained from the CP‐corrected surfaces can be safely used for the purpose of CBS extrapolations. © 2000 John Wiley & Sons, Inc. J Comput Chem 22: 196–207, 2001     

Kinetics of destruction of diisopropyl methylphosphonate in corona discharge

The kinetics of the destruction of diisopropyl methylphosphonate (DIMP) in corona discharge has been studied using a flow tubular coaxial wire dielectric barrier corona discharge reactor. The identification and quantitative determination of DIMP, its destruction intermediates, and phosphorus‐containing destruction products were performed using molecular beam mass spectrometry and gas chromatography/mass spectrometry. Active discharge power was varied in the range 0.01–5 W. The destruction products such as isopropyl methylphosphonate, methylphosphonic acid, and orthophosphoric acid were found on the reactor walls. The dependence of the extent of the destruction, D (D = 1 ? X / X₀, where X and X₀ are DIMP mole fractions at the outlet and the inlet of the reactor), on the specific energy deposition E_x (E_x = PF^?1 X₀^?1, where F is the carrier gas flow and P is the power dissipated in discharge reactor) was measured over the DIMP mole fraction range 60–500 ppm at the pressure of 1 bar and the temperature of 340 K. Over the range of the experimental conditions studied the destruction obeys the “pseudo‐first‐order” kinetic law: ln(1 ? D) = ?KE_x. Plausible mechanisms of the destruction are discussed. It was concluded that ion mechanism is the major one responsible for the destruction process. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 331–337, 2002