Isothermal compressibility and sound velocity of binary liquid systems: Application of hard sphere models

Sound velocity and density were measured in six binary liquid mixtures namely,n-heptane+toluene (I);n-heptane+n-hexane (II); toluene+n-hexane (III); cyclohexane+n-heptane (IV); cyclohexane+n-hexane (V), andn-decane+n-hexane (VI) at 298.15 K. The experimental isothermal compressibility has been evaluated from measured values of density and sound velocity. The isothermal compressibility of these mixtures has been calculated theoretically using different models for the hard sphere equation of state and also using Flory’s statistical theory. The computed values of isothermal compressibility were also compared with the experimentally evaluated values. A satisfactory agreement has been observed.     

Speeds of sound and isothermal compressibility of ternary liquid systems: Application of Flory’s statistical theory and hard sphere models

Speeds of sound and densities of three ternary liquid systems namely, toluene + n-heptane + n-hexane (I), cyclohexane + n-heptane + n-hexane (II) and n-hexane + n-heptane + n-decane (III) have been measured as a function of the composition at 298.15 K at atmospheric pressure. The experimental isothermal compressibility has been evaluated from measured values of speeds of sound and density. The isothermal compressibility of these mixtures has also been computed theoretically using different models for hard sphere equations of state and Flory’s statistical theory. Computed values of isothermal compressibility have been compared with experimental findings. A satisfactory agreement has been observed. The superiority of Flory’s statistical theory has been established quite reasonably over hard sphere models.      

Experimental study of boiling-up kinetics and superheat limit for n-hexane on solid powder-like structures

The experimental setup is described and results are presented for measuring average boiling-up lag time for superheated n-hexane mixed with solid structures (activated coal, cellulose, silica gel) as function of temperature under atmospheric pressure. The “aging” of the cell with the filler was carried out before measurements: this was about 600–1000 boiling events. We developed a new method for analysing of “aging” procedure: comparison of average flux (frequency) of boiling-up events (processing of experimental data) and the frequency of nucleation obtained from exponential model. By the end of aging of the cell with silica gel the average empirical flux reduces by factor of four relative to the “exponential” value. But for activated coal and cellulose the difference in these fluxes is about 20 %. In all experiments, the event flux was nonstationary. For n-hexane in tested systems, the margin of superheating was T _n/T _cr ≅ 0.873–0.875, although it was T _n/T _cr ≅ ≅ 0.883 for n-pentane in systems filled by nickel powder (sintered porous nickel with grains of 1.5 or 5.0 micron size) and in the presence of a smooth copper plate. The average time of boiling-up lag in n-hexane at low normalized temperatures was also smaller than for n-pentane. For all systems, the lag time is almost the same for the temperature range T _n/T _cr ≅ 0.860–0.874 (plateau). Thus, a smaller amount of superheated liquid or its division into smaller liquid elements does not result in longer liquid lifetime for superheat liquid and the maximal superheat temperature, as one could expect from the classical theory of homogeneous nucleation. Research was supported by the RF Presidential Foundation (NS-905.2003.2) and Russian Foundation for Basic Research (Grant No. 04-02-16285).     

Critical properties of nitrobenzene solutions by electric conductivity method

Electric conductivity of nitrobenzene soluted inn-hexane,n-heptane andn-octane was studied in constant and alternative field. Phase coexistence curves were determined together with the critical temperature, critical concentration and critical exponentβ for each of the systems. The measurements were performed in the temperature rangeT _s <T < (T _s + 10)K and for the concentrations of nitrobenzene between 0·2 ≲x ₂ ≲ 0·7 molar fraction.     

Dielectric behaviour of ketone-amine binary mixtures at microwave frequencies

Values of dielectric constant (ε′) and loss factor (ε″) have been experimentally determined for binary liquid mixtures of ethyl methyl ketone+ethylenediamine and methyl isobutyl ketone+ethylenediamine at 9.44 GHz microwave frequencies at 30°C. The values ofε′ andε″ have been used to evaluate the molar polarization, apparent polarization and the excess permittivities. Excess refractive index, viscosity and activation energy of viscous flow have also been estimated. These parameters have been used to explain the formation of 1:1 complexes for both the systems.     

The transformation of <Emphasis Type="Italic">n</Emphasis>-alkanes on H-forms of zeolites under supercritical conditions

The skeleton isomerization of n-butane, n-hexane, and n-heptane was studied under supercritical conditions on H-forms of zeolites mordenite, beta, and ZSM-5 over the temperature and pressure ranges 260–450°C and 80–130 atm. The isomerization of n-hexane and n-heptane was accompanied by side processes such as oligomerization and cracking. The selectivity of formation of branched isomers of these hydrocarbons did not exceed 70 and 30%, respectively. The catalyst with the most stable operation was pentasil ZSM-5, but the selectivity of formation of branched isomers on it did not exceed 30% even at 260–280°C and decreased to 3% as the reaction temperature increased to 400–450°C. The fraction of aromatization products was then more than 15%. A study of the influence of C₆–C₇ n-alkane additives on the isomerization of n-pentane on mordenite in the H-form under supercritical conditions at 260°C and 120 atm showed that a gradual decrease in the activity of this catalyst in the isomerization of n-pentane was related to the formation of heavier hydrocarbons.     

Sound velocity in binary liquid mixtures and the statistical mechanical theories

Sound velocity in three binary liquid mixtures benzene+cyclohexane (I), cyclohexane+carbontetrachloride (II) and benzene+carbontetrachloride (III) has been measured. Significant structure and Flory — Patterson theories have been employed to evaluate ultrasonic velocity in the systems. The values are in good agreement with the experimental ones. A comparative study of significant structure theory and Flory-Patterson Theory has been made. Both the theories give satisfactory results for the three liquid mixtures.     

Effects of benzene,cyclo-hexane and n-hexane addition to methane on soot yields in high-pressure laminar diffusion flames

Effects of doping high pressure methane diffusion flames with benzene, cyclo-hexane and n-hexane were investigated to assess the sooting propensity of three hydrocarbons with six carbons at elevated pressures. Amount of liquid hydrocarbons added to methane constituted 7.5% of the total carbon content of the fuel stream. The pressure range investigated extended up to 10 bar and the experiments were carried out in a high pressure combustion chamber capable of establishing stable laminar diffusion flames with various fuels at elevated pressures and was used in similar experiments previously. Temperatures and soot volume fractions were measured using the spectral soot emission technique capturing spectrally-resolved line-of-sight intensities which were subsequently inverted using an Abel type algorithm to obtain radial distributions assuming that the flames are axisymmetric. The total mass carbon flow of the fuel stream was kept constant at 0.524 mg/s in neat methane, benzene-doped methane, cyclo-hexane-doped methane, and n-hexane-doped methane flames to have tractable measurements at all pressures. Measured maximum soot volume fractions and evaluated maximum soot yields showed that benzene-doped methane flame had the higher values than cyclo-hexane doped methane flames which in turn had higher values than n-hexane doped methane flames at all pressures. Sooting propensity dependence of the three hydrocarbons on pressure can be ranked as, in descending order, n-hexane, cyclo-hexane, and benzene; however, the difference between pressure dependencies of n-hexane and cyclo-hexane was within the measurement error margins. Ratio of soot yields of benzene to n-hexane doped flames changed from about 2 at 2 bar to 1.2 at 10 bar; the ratio of benzene to cyclo-hexane doped flames showed similar trends.     

Experimental testing of liquid boiling-up homogeneity near the boundary of the attainable superheating

Results of measured average expectancy time of n-pentane and n-hexane boiling-up to the boundary of attainable superheating are presented. Experiments have been carried out in glass capillaries with substantially decreasing value of the superheated liquid volume for the preset metastable state (p, T = const). Obtained data fail to prove correlation 1 JVῑ = following from the condition of homogeneity and stationarity of the random process resulting in the superheated liquid boiling-up (J is the frequency of homogenous nucleation, V is the volume of the superheated liquid, ῑ is the average life time). Thus, experiments on superheated liquid boiling-up kinetics bound with measurements of average life time in glass capillaries cannot serve a proof of the validity of classical theory of nucleation for superheated liquids since one of the ground conditions — boiling-up homogeneity — is not met.     

The Lorentz-Lorenz function of five gaseous and liquid saturated hydrocarbons

The refractive indices of compressed gaseous and liquid ethane, propane,n-butane,n-pentane, and liquidn-hexane were measured on up to seven isotherms at temperatures between 290 K and 500 K. Densities ranged from 0.2 g/cm³ to 0.7 g/cm³ at pressures up to 170 bar. The refractive index valuesn were combined with simultaneously measured density values ?, to compute the Lorentz-Lorenz function LL =(n ²-1)M/(n ²+2) ?=A _n+B_n(?/M), whereM is the molar mass andA _n andB _n are the first and second refractive index virial coefficients. Additionally, the functions LL/z (z=pV/nRT is the compressibility factor) of ethane, propane, andn-butane were computed to determine the second refractive index virial coefficientsB _n(T). The relative uncertainty of the measured LL functions is 0.1% in most cases. At constant temperature (LL?A _n)/A_n is ≦5·10^?3 for ethane, propane, andn-butane and ≦0.02 forn-pentane andn-hexane. The greatest deviations of the LL functions from theA _n value were measured at the temperatures near the critical points. TheA _n-values show a temperature dependence which increases with increasing molar mass (maximum value: ΔA _n/ΔT=0.0044 cm³/mol · K). The slopes of the LL-function become lower and the LL maxima become smaller with increasing distance of the temperature from the critical point. TheB _n values increase linearly with reciprocal temperature.     

Experimental study of the ignition of <Emphasis Type="Italic">n</Emphasis>-hexane- and <Emphasis Type="Italic">n</Emphasis>-decane-based surrogate fuels

Surrogate fuels on the basis of mixtures of n-hexane, n-decane, and benzene are fuels alternative to petroleum motor fuels, similar to the former in thermodynamic and kinetic properties. The fact the surrogate fuels are composed of a limited number of components makes it possible to develop both detailed and global kinetic mechanisms of their ignition in mixtures with oxidizers. In turn, the possibility of the kinetic modeling of the ignition of such fuels over wide temperature and pressure ranges is of critical importance for the numerical modeling of combustion-to-detonation transition phenomena. An experimental method for measuring ignition delay times of mixtures of air with liquid fuels with low vapor pressure under normal conditions is developed and tested. In the present work, the ignition of stoichiometric mixtures of air with n-hexane, n-decane, and surrogate fuels composed of 20% n-hexane and 80% n-decane, 20% benzene and 80% n-decane, and 9.1% n-hexane, 18.2% benzene, and 72.7% n-decane is experimentally investigated in a static reactor. The ignition delay time is determined by recording pressure oscillograms at temperatures of 530–1030 K and pressures of 1–9 atm.     

Excess molar volumes and isentropic compressibilities of binary liquid mixtures containing n-alkanes at 298.15 K

Excess molar volumes (V ^E) and deviation in isentropic compressibilities (Δβ _s) have been investigated from the density ρ and speed of sound u measurements of six binary liquid mixtures containing n-alkanes over the entire range of composition at 298.15 K. Excess molar volume exhibits inversion in sign in one binary mixture, i.e., n-heptane + n-hexane. Remaining five binary mixtures, n-heptane + toluene, cyclohexane + n-heptane, cyclohexane + n-hexane, toluene + n-hexane and n-decane + n-hexane show negative excess molar volumes over the whole composition range. However, the large negative values of excess molar volume becomes domainant in toluene + n-hexane mixture. Deviation in isentropic compressibility is negative over the whole range of composition in the case of all the six binary mixtures. Existence of specific intermolecular interactions in the mixtures has been analyzed in terms of excess molar volume and deviation in isentropic compressibility.     

Environmentally benign nanomixing by sonication in high-pressure carbon dioxide

Due to the increased use of nanocomposites, mixing at nanoscale has become important. Current mixing techniques can be classified into: (a) dry mixing (mechanical mixing), (b) wet mixing, and (c) simultaneous production of mixed nanoparticles (when possible). Dry mixing is in general not effective in achieving desired mixing at nanoscale, whereas wet mixing suffers from different disadvantages like nanomaterial of interest should be insoluble, has to wet the liquid, and involves additional steps of filtration and drying. This paper examines the use of pressurized carbon dioxide having high density and low viscosity to replace the liquids (e.g., n-hexane, toluene). Ultrasound is applied to the suspension of nanopowders in gaseous and supercritical carbon dioxide where high impact collisions during sonication help mixing and the final mixture is obtained by simple depressurization. The method is tested for binary mixture of alumina/silica, silica/titania, MWNT (multiwalled carbon nanotubes)/silica, and MWNT/titania. The effects of sonication intensity and pressure on the degree of mixing are studied. Comparative study is also done with liquid n-hexane as a mixing media. Quantitative characterization (e.g., mean composition standard deviation, intensity of segregation) of mixing of alumina/silica and silica/titania is done with energy-dispersive X-ray spectroscopy, and that of MWNT/silica and MWNT/titania is done using field-emission scanning electron microscopy and day-light illumination spectrophotometry. Results show that mixing in carbon dioxide at higher ultrasound amplitudes is as good as in liquid n-hexane, and the final mixed product does not contain any residual media as in the case of liquid n-hexane.     

Acoustical and excess properties of {1-hexanol + n-hexane, or n-octane, or n-decane} at (298.15, 303.15, and 308.15) K

Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (V_m^E), molar isentropic compressibility (K_s,m), excess molar isentropic compressibility (K_s,m^E), deviation in speed of sound (u^D) from their ideal values (u^id) in an ideal mixture, and excess free volumes (V_f^E) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κ_S) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.     

Anomaly in electric resistance of binary liquids near the critical point

Electric resistance in critical solutions of nitrobenzene inn-hexane,n-heptane andn-octane was measured. The resistance near the critical point was studied and divergence in the temperature derivative measured.     

Excess molar volumes,viscosity deviations,excess isentropic compressibilities and deviations in relative permittivities of (alkyl acetates (methyl,ethyl, butyl and isoamyl) + n-hexane, + benzene, + toluene, + (o-, m-, p-) xylenes, + (chloro-, bromo-, nitro-) benzene at temperatures from 298.15 to 313.15 K

The experimental densities (ρ), dynamic viscosities (η), speeds of sound (υ) and relative permittivities (ε_r) of thirty six binary mixtures of esters (methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate) + organic solvents (n-hexane, benzene, toluene, o-, m-, p- xylenes), + halogenated benzene (chloro-, bromobenzene), + nitrobenzene have been measured over the complete composition range at atmospheric pressure and temperatures (298.15 to 313.15 K). The excess molar volumes, V_m^E, excess isentropic compressibilities, κ_s^E, deviations in relative permittivities, δε_r have been calculated and fitted to Redlisch–Kister type equation. The dynamic and kinematic viscosities have been correlated through Grunberg–Nissan and MacAllister equations. The qualitative analysis of various functions revealed that i.) esters lose their dipolar association in presence of inert and unlike n-hexane, ii.) specific but weaker n…π type interactions predominate in binary mixtures of esters + aromatic organic solvents and iii.) weak electron donor–acceptor complexes predominate in the mixtures of esters with halogenated and nitrated benzene.     

Vacuum ultraviolet absorption spectra of aromatic molecules in solution

The absorption spectra of benzene, naphthalene, azulene, N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), pyrene, and fluoranthene were measured in liquid perfluoro-n-hexane (PFn-H) in the range 35 000–65 000 cm^?1 and in liquid n-pentane (n-Pt) in the range 35 000–59 000 cm^?1, using a 150-μm-thick cell. The absorption spectra in PFn-H show more structure than those in n-Pt and because they are extended in the Rydberg transition region may be used to separate Rydberg from core transitions in the gaseous spectra of the molecules studied. The transmission spectra for PFn-H, n-Pt, and some of the most commonly used hydrocarbon solvents are presented also.     

Laser light scattering technique for non-invasive<Emphasis Type="Italic">in situ</Emphasis> simultaneous measurements on elastic constants and viscosity coefficients of nematic liquid crystals

The laser light scattering technique for non-invasivein situ simultaneous measurements on elastic constants and viscosity coefficients of nematic liquid crystals is introduced. By measuring the autocorrelation function of the scattered light from nematic liquid crystals at different scattering angles, the splay and twist elastic constantsK ₁₁ andK ₂₂ are obtained from the amplitudes of the autocorrelation function, and the viscosity coefficients ofη _Splay andη _Twist are determined using the viscoelastic ratiosK ₁₁/η _Splay andK ₂₂ η _Twist from the telaxation parameters of the two modes.     

Pressure broadened calculations of the OCSJ = 1 → 2 line by non-polar perturbers

Microwave spectral line widths of the transitionJ = 1 → 2 of OCS perturbed by non-polar perturbers,n-hexane, cyclohexane,n-heptane, carbon disulphide, carbon tetrachloride and benzene have been calculated using a recent theory of Mehrotra and Boggs.     

Cluster Structure of Liquid Alcohols,Water, and <Emphasis Type="Italic">n</Emphasis>-Hexane

The processes of cluster formation in liquid alcohols, water, methanol, n-hexanol, and n-hexane have been investigated by the method of flicker-noise spectroscopy. Two types of clusters — clusters with a close-packed structure and clusters with a loose structure — have been detected. The energy of formation of different clusters in methanol and n-hexane ranges, respectively, from −250 to +250 J/mole and from −50 to +50 J/mole. The smallest clusters of methanol, n-hexanol, water, and n-hexane consist, respectively, of six, two, eleven, and two molecules, and their largest clusters represent oscillators consisting, respectively, of 50,400, 17,200, 93,500, and 33,150 molecules at 274 K. In methanol at 271 K, more than 44 types of clusters consisting of 6, 97, 152, 219, 297, 492, 1029, 1368, 1560, etc. molecules were detected. In n-hexanol at 273 K, 57 types of clusters were detected. Models of small clusters are proposed. In water, the content of close-packed clusters is maximum at 277 K. The energy of formation/decomposition of small clusters in water ranges from −0.4 to +0.4 kJ/mole and increases with increase in the water temperature. The hysteresis of transformation of the (H₂O)₂₈₀ cluster in the process of heating and cooling of water in the temperature range 273–280 K was detected. Series of energy spectra of clusters in liquids at different temperatures are presented and discussed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 305–312, May–June, 2005.