Isothermal vapor—liquid equilibrium of ternary mixtures formed by 1-propanol,acetonitrile and benzene

Vapor—liquid equilibrium data are presented for the ternary system 1-propanol-acetonitrile-benzene, at 45°C. The experimental vapor—liquid equilibrium results of the three constituent binary systems are well reproduced with the UNIQUAC associated-solution model and the ternary results are compared with those calculated from the model with binary parameters alone. Ternary prediction of liquid—liquid equilibria is given for the 1-propanol-acetonitrile-n-hexane and 1-propanol—acetonitrile-n-heptane systems at 25°C.     

Vapor–liquid equilibria for the system 1-propanol+n-hexane near the critical region

Vapor–liquid equilibria and critical point data for the system 1-propanol+n-hexane at 483.15, 493.15, 503.15 and 513.15 K are reported. The critical pressures determined from the critical opalescence of the mixture were compared with published data for the system 2-propanol+n-hexane. Phase behavior measurements were made in a modified circulating type apparatus with a view cell. These mixtures are highly nonideal because of the hydrogen bonding of 1-propanol. Modeling of the experimental data has been performed using the multi-fluid nonrandom lattice fluid with hydrogen-bonding (MF-NLF-HB) equation of state and the Peng–Robinson–Stryjek–Vera (PRSV) equation of state with Wong–Sandler mixing rule. The critical points and the critical locus were also calculated.     

Comparison of Separation Performances of Cellulose-Based Chiral Stationary Phases in LC Enantioseparation of Aminonaphthol Analogues

The enantiomers of 1-(α-aminoarylmethyl)-2-naphthol, 1-(α-aminoalkyl)-2-naphthol and 2-(α-aminoarylmethyl)-1-naphthol analogues were separated on tris(3,5-dimethylphenyl)carbamoyl cellulose-based CelluCoat and Chiralcel OD-H chiral stationary phases, with n-heptane/alcohol or n-hexane/alcohol as mobile phase. The experimental data are utilised to discuss the effects of the mobile phase composition, the nature of the alcoholic modifier and the specific structural features of the analytes (1- or 2-naphthol analogues with aryl or alkyl substituents) on the retention and separation. The separation performances of CelluCoat and Chiralcel OD-H columns were compared. Due to its high resolution ability and its effectivity, CelluCoat proved to be a good choice for the enantiomeric separation of aminonaphthol analogues.     

Isothermal measurements of vapor-liquid equilibria for three n-alkane-chloroalkane mixtures

Results of isothermal vapor-liquid equilibrium (VLE) measurements for 1-chlorobutane with n-hexane and n-heptane at three temperatures and for 1,2-dichloroethane with n-heptane at two temperatures are reported.New constants of the Antoine vapor pressure equation for 1,2-dichloroethane are presented. The consistency of the new vapor-pressure data with published experimental data of heat of vaporization is checked.The VLE data are used for the determination of group interaction parameters of UNIFAC and of the quasichemical group surface interaction model (QUAGSIM).     

Preferential Solvation in Mixed Solvents

The Kirkwood–Buff integrals and the volume-corrected preferential solvation parameters for the first solvation shell of binary mixtures of tetrahydrofuran with many organic solvents, calculated from reported thermodynamic data at the temperatures for which these data were available, are reported. The co-solvents include c-hexane, methyl-c-hexane, n-heptane, i-octane, benzene, toluene, ethylbenzene, 1-chlorobutane, dichloromethane, 1,2-dichloroethane, chloroform, 1,1,1-trichloroethane, tetrachlorom-ethane, tetrachloroethene, hexafluoro benzene, ethanol, 1-propanol, 2-propanol, dibutyl ether, acetic acid, acetone, dimethyl sulfoxide, tetramethylene sulfone (sulfolane), acetonitrile, pyrrolidine, and triethylamine. The preferential solvation parameters of these mixtures are discussed in terms of the interactions that occur.     

Activity coefficients of hydrocarbon solutes at infinite dilution in the ionic liquid, 1-methyl-3-octyl-imidazolium chloride from gas–liquid chromatography

Activity coefficients for hydrocarbon solutes at infinite dilution in 1-methyl-3-octyl-imidazolium chloride have been measured using the medium pressure gas–liquid chromatography method. The hydrocarbon solutes used were n-pentane, n-hexane, n-heptane, n-octane, 1-hexene, 1-heptene, 1-octene, 1-hexyne, 1-heptyne, 1-octyne, cyclopentane, cyclohexane, cycloheptane, benzene, and toluene. Activity coefficients at infinite dilution were determined at the following three temperatures (298.15, 308.15, and 318.15) K. Selectivities for benzene and the hydrocarbons are presented and the results indicate that 1-methyl-3-octyl-imidazolium chloride is a reasonable solvent for the separation of an alkane or an alkene from benzene.     

Studies on the relative temperature viscosity coefficient of nitrobenzene in n-hexane and n-heptane near the temperature of phase separation

The viscosity coefficient η of nitrobenzene in n-hexane and n-heptane was measured as a function of concentration and temperature near the te     

Peculiarities of asphaltene precipitation in <Emphasis Type="Italic">n</Emphasis>-alkane-oil systems

n-Pentane-, n-hexane-, and n-heptane-insoluble asphaltenes obtained via a standard procedure by precipitating from oil solutions in n-pentane, n-hexane, and n-heptane, respectively, as well as n-pentane/n-hexane/n-heptane-insoluble and n-heptane/n-hexane/n-pentane-insoluble asphaltene constituents prepared through successive washing (fractional dissolution) of n-pentane-insoluble asphaltenes with n-hexane and n-heptane and n-heptane-insoluble asphaltenes with n-hexane and n-pentane, respectively, are studied. Asphaltenes and their constituents extracted from three oils distinguished by high contents of asphaltenes, resins, and paraffins, respectively, are investigated by ¹H NMR spectroscopy in carbon tetrachloride solutions. It is established that the mass fractions and the fragment compositions of asphaltenes and their constituents depend on both the type of oil and the procedure of their preparation; i.e., the precipitation from n-alkane-oil systems or the extraction through the successive washing with a series of n-alkanes. The obtained experimental data made it possible to formulate a hypothesis according to which the precipitation of asphaltenes from oils is controlled by not only the dissolving power of a solvent with respect to molecular components of initial oils, but also (and primarily) by the dissolving power of a solvent with respect to supramolecular structures of asphaltenes formed in n-alkane-oil systems.     

Vibronic coupling of pyrene in the first ππ* excited state

The two-photon fluorescence excitation spectrum of pyrene in n-hexane and n-heptane matrices has been measured at 10 K in the region of the first electronic transition (26800–30200 cm^?1). The spectrum consists of a rich number of sharp bands, being in general better resolved in n-hexane than in n-heptane matrix. Shpol'skii multiplets have been observed for the most intense bands. A strong two-photon band dominates the spectrum = 1495 cm^?1 from the 0—0 line and was assigned to B_1u × b_1u = A_g symmetry. Other weaker vibronic origins occur in the spectrum which were correlated to vibrational modes of b_1u, b_2u, b_3u and a_u symmetry. Intense vibronic bands are observed close to the origin of the second electronic transition and were interpreted as combination bands of B_1u × b_1u × b_3g symmetry. A two-photon vibronic theory to account for their intensity is proposed where the electronic moment is linearly expanded in powers of the nuclear displacements.     

A comparison of phototautomerism in different sites of free-base porphin (H2P) in n-alkane crystals

Selective laser-induced phototautomerism of free-base porphin in different n-alkanes (n-hexane, n-heptane, n-octane, nnonane, n-decane, n-undecane and n-dodecane) has been used to identify tautomer splittings in a number of sites in polycrystalline samples at 2 K. Pairs or lines arising from the two molecular orientations in each site can be reversibly transformed into each other. In the odd n-alkanes the occupation of different sites was not dependent on the rate at which the samples were frozen, but in the even n-alkanes metastable sites were only occupied following rapid quenching.     

QCM gas phase detection with ceramic materials—VOCs and oil vapors

Titanate sol–gel layers imprinted with carbonic acids were used as sensitive layers on quartz crystal microbalance. These functionalized ceramics enable us detection of volatile organic compounds such as ethanol, n-propanol, n-butanol, n-hexane, n-heptane, n-/iso-octane, and n-decane. Variation of the precursors (i.e., tetrabutoxy titanium, tetrapropoxy titanium, tetraethoxy titanium) allows us to tune the sensitivity of the material by a factor of 7. Sensitivity as a function of precursors leads to selective inclusion of n-butanol vapors down to 1 ppm. The selectivity of materials is optimized to differentiate between isomers, e.g., n- and iso-octane. The results can be rationalized by correlating the sensor effects of hydrocarbons with the Wiener index. A mass-sensitive sensor based on titanate layer was also developed for monitoring emanation of degraded engine oil. Heating the sensor by a meander avoids vapor condensation. Thus, a continuously working oil quality sensor was designed.     

p, T, x, y data of benzene + n-hexane and cyclohexane + n-heptane systems

The isothermal vapour—liquid equilibria of the benzene + n-hexane and cyclohexane + n-heptane systems have been studied using a dynamic method. The thermodynamic consistency of the data has been tested and the prediction from several empirical and semitheoretical models have been compared with the experimental values of different excess properties.     

Influence of the host on vibronic relaxation: a study of free-base porphin in a series of n-alkanes by photochemical hole-burning

Photochemical hole-burning is used to determine the relaxation times of vibronic bands of the S₁ ← S₀ transition to free-base porphin in different substitutional sites of n-hexane, n-heptane, n-octane and n-decane at 1.6 K. The vibronic relaxation depends strongly on site and host. A correlation between the n-alkane chain length and the vibronic relaxation time is observed.     

Liquid–Liquid Equilibria of Oxygenate Fuel Additives with Water at 298.15 K: Ternary and Quaternary Aqueous Systems of Diisopropyl Ether and Hydrocarbons with 2-Propanol

Experimental tie-line data were determined for one ternary system, water + diisopropyl ether + n-heptane and two quaternary systems, water + diisopropyl ether + 2-propanol + n-heptane or toluene at 298.15 K and ambient pressure. The experimental liquid–liquid equilibrium data were successfully correlated using a modified UNIQUAC model with ternary and quaternary mixture parameters, in addition to the binary ones. The calculated results were also compared with those obtained from an extended UNIQUAC model of Nagata [Fluid Phase Equilib. 54, 191 (1990)].     

Limiting activity coefficients of hydrocarbons in phenol

Temperature dependence of the limiting activity coefficients of saturated (n-hexane, n-heptane, n-octane, and cyclohexane) and aromatic (benzene, toluene, ethylbenzene, o-xylene) hydrocarbons in phenol was studied in the temperature range 308–348 K by the headspace analysis method.     

Phase equilibria study of the (N-octylisoquinolinium thiocyanate ionic liquid + aliphatic and aromatic hydrocarbon,or thiophene) binary systems

Binary liquid + liquid phase equilibria for 8 systems containing N-octylisoquinolinium thiocyanate, [C₈iQuin][SCN] and aliphatic hydrocarbon (n-hexane, n-heptane), cyclohexane, aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene) and thiophene have been determined using dynamic method. The experiment was carried out from room temperature to the boiling-point of the solvent at atmospheric pressure. For the tested binary systems the mutual immiscibility with an upper critical solution temperature (UCST) for {IL + aliphatic hydrocarbon, or thiophene} were observed. The immiscibility gap with lower critical solution temperature (LCST) for the {IL + aromatic hydrocarbon} were determined. The parameters of the LLE correlation equation for the tested binary systems have been derived using NRTL equation. The phase equilibria diagrams presented in this paper are compared with literature data for the corresponding ionic liquids with N-alkylisoquinolinium, or N-alkylquinolinium cation and with thiocyanate – based ionic liquids. The influence of the ionic liquid structure on mutual solubility with aliphatic and aromatic hydrocarbons and thiophene is discussed.     

Enthalpy of hydrogen bonded alcohol-butyl amine complexes by a simpler calorimetric method

The heats of mixing ofn-butyl amine with methanol andn-propanol have been determined at 30° C and the enthalpies of alcohol-amine complex formation have been calculated by thermochemical cycle. The enthalpies of complex formation of butyl amine with methanol andn-propanol were found to be-44.3 kJ/mole and-39.4 kj/mole respectively. The heats of mixing of synthetically prepared 1:1 molar mixtures of n-butyl amine with methanol, ethanol andn-propanol withn-hexane have also been determined at 30° C. The enthalpy of amine-alcohol complexes was obtained from the partial molar heats of dissociation of the complexes inn-hexane. The values agree with those obtained by the thermochemical cycle method. NCL Communication No. 2561.     

Heat capacities of binary mixtures of n-heptane with hexane isomers

Volumetric heat capacities were measured for binary mixtures of n-heptane with n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane at 298.15 K in a Picker flow microcalorimeter. The results were combined with previously published excess molar volumes to obtain excess molar isobaric heat capacities. Use of the Flory theory of mixtures to interpret the latter is discussed.     

Catalytic dechlorination of aromatic chloride with supported palladium catalysts in alkaline 2-propanol: influence of hydrocarbon solvents

Summary Catalytic dechlorination of p-chloroanisole (p-chloromethoxybenzene) was carried out in a solution of NaOH in 2-propanol in the presence of Pd/Al₂O₃ or Pd/C at 40°C. When aromatic hydrocarbons such as toluene or benzene were added to the solution, the dechlorination rates were strongly suppressed. However, aliphatic hydrocarbons such as n-hexane or cyclohexane hardly affected the dechlorination rates.     

Speed of sound,molar volume,and molar isobaric heat capacity for binary liquid mixtures: analysis in terms of van der Waals's one-fluid theory

The speed of sound and excess molar isobaric heat capacity at 298.15 K, and the excess molar volume at 303.15 K are reported for (n-dodecane + n-hexane). The results, in combination with the excess molar volume at 298.15 K published previously, are used to obtain the interaction parameters a₁₂ and b₁₂ for the mixture treated as a pure fluid obeying a generalized van der Waals's equation of state. Similar analyses, using results from our previous investigations, are presented for (di-n-propylether + n-heptane) and (benzene + cyclohexane).