The self-association of ethanol in non-polar solvents

The self-association of ethanol in solutions of n-hexane, cyclopentane, cyclohexane, carbon tetrachloride and benzene is studied on the basis of heat of dilution data published in the literature. The tetramer formation model fits the experimental data better than other self-association models. The corresponding self-association constants, K_1,4, and heats of reaction, ΔH_1,4, are calculated. The solvent effect is studied using the solvent polarity factor, E_T, and the existence of a linear dependance of log K_1,4 on E_T values is shown.     

Evaluation of the ionic liquids 1-alkyl-3-methylimidazolium hexafluorophosphate as a solvent for the extraction of benzene from cyclohexane: (Liquid + liquid) equilibria

In the catalytic hydrogenation of benzene to cyclohexane, the separation of unreacted benzene from the product stream is inevitable and essential for an economically viable process. In order to evaluate the separation efficiency of ionic liquids (ILs) as a solvent in this extraction processes, the ternary (liquid + liquid) equilibrium of 1-alkyl-3-methylimidazolium hexafluorophosphate, [C_nmim][PF₆] (n = 4, 5, 6), with benzene and cyclohexane was studied at T = 298.15 K and atmospheric pressure. The reliability of the experimentally determined tie-line data was confirmed by applying the Othmer–Tobias equation. The solute distribution coefficient and solvent selectivity for the systems studied were calculated and compared with literature data for other ILs and sulfolane. It turns out that the benzene distribution coefficient increases and solvent selectivity decreases as the length of the cation alkyl chain grows, and the ionic liquids [C_nmim][PF₆] proved to be promising solvents for benzene–cyclohexane extractive separation. Finally, an NRTL model was applied to correlate and fit the experimental LLE data for the ternary systems studied.     

The yield of solvent excited states in the radiolysis of cyclohexane solutions

It is confirmed by pulse radiolysis that emitting solvent excited states are produced in the radiolysis of n-hexane, methylcyclohexane and cyclohexane. The emission is quenched by benzene and benzene emission appears. Applying stern - volmer kinetics to emissions from solvent, benzene and toluene in cyclohexane a very high energy transfer rate constant, viz., k = 2.8 × 10¹¹M⁻¹ sec⁻¹ is obtained. The yield of the excited state of cyclohexane is not greater than 0.3, and it is concluded that the major part of the excited states of other aromatics produced in cyclohexane solutions comes from ion neutralisation.     

Solvent effect on u.-vis and EPR spectra and on the relative stability of mononuelear and binuclear complexes of Cu(II) acetate with pyridine derivatives

Electronic (298.2 K) and ESR (298 and 77 K) spectra have been measured for Cu(O₂CMe)₂ solutions in pyridine derivative (L)-solvent (S) binary mixtures (L = pyridine, 3-chloropyridine, 2-chloropyridine; S = n-hexane, n-heptane, cyclohexane, benzene, chlorobenzene, carbon tetrachloride, propylene carbonate). The results are interpreted in terms of the equilibrium between mononuclear and binuclear complexes: 2Cu(O₂CMe)₂ ⇌ Cu₂(O₂CMe)₄L₂ + 2L.The calculated quotient ofthe activity coefficients ofthe two forms strongly depends on the L-ligand activity in the solutions (preferential salvation by L) and on the solvent properties. Chlorobenzene, benzene and carbon tetrachloride compete with pyridine for solvation. The ln of the activity coefficient quotient varies linearly with the solubility parameter of the solvent, δ, while no satisfactory correlation with the polarity parameter (ε − 1)/(2ε + 1) has been found. The solvent effect on electronic spectra (λ_max, g3_max) is stronger for mononuclear, more flexible, complexes than for binuclear ones.     

Solvent effects on relaxation of the 1B2u state of benzene

Values of triplet yields for dilute solutions of benzene in methylcylohexane, cyclohexane, methanol, ethanol, acetonitrile, perfluoro-n- hexane, and water, and also fluorescence yields and lifetimes in perfluoro-n-hexane are reported. The calculated rate constants for fluorescence and intersystem crossing are only slightly affected by solvent, except for water. The enhancement of “internal conversion” by increasing solvent polarity is interpreted as a result of an increase in the pre-exponential factor for a possible ¹(π,π^*) → ¹(σ,π^*) transition.     

Raman study of vibrational relaxation of cyclohexane in benzene solutions

The Raman profiles of the ν₅ mode (802 cm^?1) of cyclohexane, ν₅ (723 cm^?1) of cyclohexane-_d12 and ν₂ (992 cm^?1) of benzene and its deuterated analogs have been measured as a function of concentration in the benzene—cyclohexane liquid system. The vibrational time correlation functions of cyclohexane in benzene solutions have been calculated by Fourier inversion of isotropic band contours. The concentration dependence of the experimental vibrational correlation times computed from the correlation functions and from the half width at half height have been compared with that predicted theoretically for various mechanisms of band broadening. We have tested the Fischer—Laubereau dephasing model and the Knapp—Fischer concentration-fluctuation model. We have found that the latter model reproduces well experimental data only for the ν₂ mode of benzene in solution.     

Picosecond time-resolved spectroscopy and the intersystem crossing rates of anthrone and fluorenone

The rise time of the T_n ← T₁ absorption of anthrone in benzene is determined to be 70 ps. The mechanism of efficient intersystem crossing of anthrone has been discussed and is compared with that of benzophenene. The rise time of fluorenone has been found to be sensitive to solvent, changing from 140 ps in cyclohexane to 12 ns in acetone. This tendency is explained in terms of the change in the character of the lowest excited singlet state of fluorenone from ππ^* in acetone to nπ^* in cyclohexane.     

Preparation of multifunctional organolithium initiator in cyclohexane solutions

Multifunctional organolithium initiator was prepared in cyclohexane solvent.The process started with adding the cyclohexane solution of butadiene to naphthalene-lithium in batches to produce butadiene oligomer dilithium with 4-8 butadiene repeating units.In the first feeding,the maximum loading of cyclohexane and the minimum concentration of butadiene cyclohexane solution must be controlled under V_cyclohexane≤1.33V_THFand p≥40.6C_N.Then,SnCl₄ was added and eventually the multifunctional organolithium initiator containing Sn atom was synthesized through coupling reaction. Experiment results showed that adding the cyclohexane solution in batches was effective in overcoming some difficulties, such as insolubility of naphthalene-lithium in cyclohexane,low efficiency of naphthalene-lithium in initiating butadiene.In practice,benzene can be replaced by cyclohexane completely,which can not only reduce environmental pollution from benzene,but also overcome the difficulty of solvent recovery caused by similar boiling point between benzene and cyclohexane.Prepared with multifunctional organolithium containing Sn atom as initiator,the star-shaped solution polymerized styrene-butadiene rubber（star S-SBR）with better vulcanization performances,lower rolling resistance and higher wet-skid resistance was obtained.     

Solvent effect on the synthesis of monodisperse amine-capped Au nanoparticles

A remarkable solvent effect in a single-phase synthesis of monodisperse amine-capped Au nanoparticles is demonstrated.Oleylamine-capped Au nanoparticles were prepared via the reduction of HAuCU by an amine-borane complex in the presence of oleylamine in an organic solvent.When linear or planar hydrocarbon(e.g.,n-hexane,n-octane,1-octadecylene,benzene,and toluene) was used as the solvent, high-quality monodisperse Au nanoparticles with tunable sizes were obtained.However,Au nanoparticles with poor size dispersity were obtained when tetralin,chloroform or cyclohexane was used as the solvent.The revealed solvent effect allows the controlled synthesis of monodisperse Au nanoparticles with tunable size of 3-10 nm.     

Quaternary liquid—liquid equilibrium. Cyclohexane—ethanol—benzene—acetonitrile

Nagata, I., 1986. Quaternary liquid—liquid equilibrium. Cyclohexane—ethanol—benzene—acetonitrile. Fluid Phase Equilibria, 26: 59–68.Experimental liquid—liquid equilibrium results are presented for the ternary acetonitrile—ethanol—cyclohexane and the quaternary cyclohexane—ethanol—benzene—acetonitrile systems at 25°C. The results agree well with the calculated values derived from the extended UNIQUAC equation (Nagata) with parameters from phase equilibrium data for the constituent binary mixtures or ternary tie-line data sets.     

Infrared spectra and configuration of N,N'-diaryl-thioureas

The conformation of the —NH—CS—NH— grouping in a series of N,N'-diarylthioureas some of which possess a marked anti-viral activity is studied using IR spectral data. The results indicate that in organic solvents (CCl₄, CHCl₃, C₂C1₄, CH₂C1₂) the compounds studied participate in an equilibrium between several isomeric forms arising from the possibility of a cis or trans structure of the —CS—NH— groups. The increased solvent polarity favours the cis conformation.     

Reactions of N-bromohexamethyldisilazane with triorganylsilanes

Reactions of N-bromohexamethyldisilazane (Me₃Si)₂NBr with Si-H compounds of the general formula RR′₂SiH yield up to 90% of unsymmetrical disilazanes (Me₃Si)₂NSiRR′₂ and bromotrimethylsilane. An unexpected solvent effect on the reaction conditions is revealed: In benzene the products are formed already on mixing, whereas in cyclohexane, under UV irradiation only.     

Sorption of organic vapors by polystyrene

Activity coefficients of benzene, toluene, cyclohexane, carbon tetrachloride, chloroform, and dichloromethane in binary solutions with polystyrene at 23.5°C have been determined using a piezo-electric sorption apparatus. The investigated solvent concentration ranges were 15 to 39 wt % for benzene, 14 to 29 wt % for toluene, 15 to 28 wt % for cyclohexane, 26 to 38 wt % for carbon tetrachloride, 24 to 46 wt % for chloroform, and 21 to 41 wt % for dichloromethane. The polystyrene (weight-averaged) molecular weights were 1.1 × 10⁵ and 6.0 × 10⁵ g/gmole. The weight-fraction activity coefficients (Ω₁ = a₁/w₁) of cyclohexane, toluene, and carbon tetrachloride in polystyrene solutions determined in this work agree within experimental error with previously published values determined by measurement of vapor pressure lowering and vapor absorption by thin films. We find disagreement, at low solvent concentrations, between our results for benzene and chloroform and previously published results. We have analyzed our results using Flory's version of corresponding-states polymer solution theory. The theory can account, qualitatively, for the cyclohexane and carbon tetrachloride results. It cannot account for the toluene, benzene, dichloromethane, or chloroform results.     

Relationships between Allerhand and Schleyer's G scale and other solvent polarity and acidity parameters

Values of Allerhand and Schleyer's solvent G parameter for 36 solvents have been correlated with solvent polarity—polarizability properties as well as parameters of solvent acidity. The equations found permit the extension of the G scale to more solvents and quantification of the influence on G of both solvent polarity—polarizability and acidity.     

On the relation between the solvent parameters and the physical properties of methyl-4,6-O-benzylidene-α-d-glucopyranoside organogels

This paper reports the mechanisms of gel formation, the thermal properties and the microstructures of the networks of the gels composed of methyl-4,6-O-benzylidene-α-d-glucopyranoside and selected organic solvents: p-xylene, benzene, toluene, diphenyl ether and tetraethoxysilane. The Fourier transform infrared measurements together with simulation spectra, the air bath method and Polarized Optical Microscopy were employed in our studies. The experimental data show that the solvent has an influence on the microstructure of the gel network but there is no predictable influence of the solvent polarity on the shape of the formed gelator aggregates and correspondingly on the fibrous assemblies as revealed by the different microstructure of the gel network. Independently of the solvent polarity, the studied gelator, like other methyl-4,6-O-benzylidene derivatives of monosaccharides, formed gels through the formation of a hydrogen-bond network. The solvent parameters, such as the dielectric constant, Hildebrand solubility parameter, the polarity scale E_T and the Kamlet–Taft parameters were considered to quantify solvent effects on the gelation. The conclusions about the correlations are of interest but only to this particular sugar based gels.     

Solvent effects on hydrogen bond formation

Enthalpies of solution have been used to calculate transfer enthalpies for phenol, pyridine, and DMSO between the solvent cyclohexane and the solvents CCl₄, benzene, and CHCl₃. By use of model compounds, enthalpies due to interactions with phenol, pyridine, and DMSO have been determined. These enthalpies are used to calculate the effect of solvation relative to cyclohexane on hydrogen bonded complexes in CCl₄ and benzene solvents. Correlations with enthalpies due to interactions and frequency shifts for the hydroxyl stretch in these solvents have also been made.     

Influence of ionization density on radiolysis of cyclohexane-benzene mixtures

Cyclohexane-benzene mixtures were irradiated by ²¹⁰Po-α-radiation (LET = 200 eV/nm) with the effective energy of 3 MeV and the results were compared with those obtained by 1.25 MeV λ-irradiation of ⁶⁰Co (LET = 0.2 eV/nm). While during λ-irradiation—similarly to the data known from the literature—the G(c-C₆H₁₀) and the G((c-C₆H₁₁)₂) values were decreased even by a small amount of benzene, the yields of both products obtained by α-irradiation were in the same range practically constant, and began to decrease only above the benzene concentration of 0.3 mol dm^-3 (about 3 electron %).The “protection” in the case of λ-irradiation was interpreted by positive ion scavenging, S₁ excited cyclohexane molecule quenching and thermal H atoms scavenging. The low efficiency of all these three components of “protection” in α-radiolysis is attributed principally to the very high concentration of intermediates in the track/core compared to the relatively low concentration of benzene.The conclusions were also supported by comparison with the data obtained in cyclohexane-iodine systems.     

Growth of a faujasite-type zeolite membrane and its application in the separation of saturated/unsaturated hydrocarbon mixtures

Faujasite type zeolite membranes were synthesized on porous ceramic alumina supports by using direct (in situ) and secondary (seeded) growth methods. In the secondary growth method a seed layer of ZSM-2 nanocrystals (prepared according to a report by Schoeman et al. J. Colloid Interface Sci. 1995, 170, 449–456) was deposited on the surface of the support before the hydrothermal growth. For both in situ and secondary growth, the mixture composition was 4.17 Na₂O:1.0 Al₂O₃:10 TEA (triethanol ammonium):1.87 SiO₂:460 H₂O. X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron microprobe analysis (EPMA), indicate well intergrown 5–30 μm thick FAU films with Si/Al ∼1–1.5. The separation of saturated/unsaturated hydrocarbon mixtures is demonstrated over a range of temperatures (40–160°C). The mixtures examined (and the corresponding equimolar mixture separation factors) are benzene/cyclohexane (160), benzene/n-hexane (144), toluene/n-heptane (45), propylene/propane (6.2), and ethylene/methane (8.4). In all cases, the membranes are unsaturated hydrocarbon permselective. With equimolar feed mixtures (5 kPa/5 kPa benzene/cyclohexane) and in the temperature range 65–160°C, the membranes exhibit separation factor of 20–160 with the benzene flux in the range 10⁻⁴–10⁻³ mol m⁻² s⁻¹. Decreasing the total feed partial pressure (0.31/0.31 kPa benzene/cyclohexane) reduces both separation factor (12) and benzene flux. Similar trend is observed when the benzene/cyclohexane ratio in the feed mixture (0.5/9.5 kPa benzene/cyclohexane) is reduced. A sorption diffusion model based on the Stefan–Maxwell formulation has also been employed to show that the benzene/cyclohexane separation can mainly be attributed to differences of their adsorption properties.     

Ultrasensitive fluorescent probe for the hydrophobic range of solvent polarities

The new 3-hydroxychromone derivative 2-(6-diethylaminobenzo[b]furan-2-yl)-3-hydroxychromone (FA) displays a dramatic solvent-dependent transformation of fluorescence spectra in the range of low-polarity solvents. The two well-separated emission bands change their relative intensities so that the short-wavelength band being of a very low intensity in hexane becomes dominant in the more polar ethyl acetate and trichloromethane. We suggest the participation in this effect of excited-state intramolecular proton transfer, which is characteristic for other 3-hydroxychromone and 3-hydroxyflavone derivatives, in the range of solvents of much higher polarities. Because of these unique properties, a number of spectroscopic parameters (positions of absorption and two fluorescence maxima, the ratio of their intensities and the fluorescence quantum yield) can be measured in this solvent range with multiparametric analysis of the data. In terms of solvent polarity, the shifts in both emission bands and their intensity ratio demonstrate a good correlation with empirical polarity scales E_T^N, P_y and SPP, while the absorption spectra reveal some deviations for the tested oxygen-containing solvent molecules. A good cross-correlation is observed between fluorescence spectral shifts and the ratio of band intensities. The latter provides the means for a dramatic amplification of solvent response. Thus, a new approach for ultrasensitive scaling and probing the solvent polarity in the low-polararity range can be suggested. It involves very simple ratiometric measurements at two emission bands and can be posed for a variety of applications. We present examples of these applications for distinguishing of polarities between methylated benzene derivatives, for quantitative assay of polar impurities in low-polar solvents and for detection of the changes of solvent polarity as a function of temperature.     

The influence of molecular interactions on polymerization—IV: Copolymerization of 2-naphthyl methacrylate and methyl methacrylate in solvents with different dielectric constants

The copolymerization of 2-naphthyl methacrylate (2-NM) with methyl methacrylate (MMA) initiated by 2,2′-azoisobutyronitrile in carbon tetrachloride, chloroform, benzene, acetone and acetonitrile was investigated. The reactivity ratios determined by the methods of Fineman-Ross and Kelen-Tüdős are: in carbon tetrachloride—r_2-NM = 2.46 ± 0.25, r_MMA = 0.61 ± 0.06; chloroform—r_2-NM = 2.71 ± 0.30, r_MMA = 0.60 ± 0.06; benzene—r_2-NM = 2.62 ± 0.44, r_MMA = 0.63 ± 0.11; acetone—r_2-NM = 4.13 ± 0.45, r_MMA = 0.60 ± 0.06 and acetonitrile—r_2-NM = 3.70 ± 0.30, r_MMA = 0.62 ± 0.05.The dependence of the reactivity ratios on the solvent is explained on the basis of formation of complexes between the electron-donating naphthalene rings and the electron-accepting methacrylic double bonds, as indicated by NMR studies.