Vapour pressures of n-pentane determined by comparative ebulliometry

The vapour pressures of n-pentane have been measured using comparative ebulliometry with water as the reference substance. The measurements cover the temperature and pressure ranges 309 K and 102 kPa to 456 K and 2728 kPa. When combined with selected literature results, the range was extended downwards to a temperature and pressure of 268.8 K and 19.9 kPa and the combined data sets were correlated by a Wagner-type equation with a standard deviation of 18 Pa in the vapour pressure. The critical pressure was treated as an adjustable parameter and the value p_c = 3367.4 kPa was obtained using a selected critical temperature, T_c = 469.7 K. The calculated normal boiling temperature was T_b = 309.207 K and an extrapolation to the triple point temperature T_tp = 143.48 K predicted a pressure of p_tp = 0.078 Pa.     

Vapour pressures of selected organic compounds down to 1 mPa,using mass-loss Knudsen effusion method

A recently developed Knudsen effusion apparatus was improved and used for measurements of vapour pressures of selected organic compounds. Calorimetric studies were conducted using a Calvet-type calorimeter, complementing the information obtained for the vapour pressures and facilitating the modelling and analysis of the data.Vapour pressures of benzoic acid, a reference substance, were determined at temperatures between 269 K and 317 K, corresponding to a pressure range from 2 mPa to 1 Pa, extending the range of results available in the literature to lower pressures. Benzanthrone was studied between temperatures 360 K and 410 K (5 mPa–1 Pa) in order to test the apparatus at higher temperatures.Values presented in the literature for the vapour pressure of solid n-octadecane, one of the most promising compounds to be used as “phase change material” for textile applications, were found inconsistent with the triple point of the substance. Sublimation pressures were measured for this compound between T = 286 K and 298 K (2–20 mPa) allowing the correction of the existing values. Finally, vapour pressures of diphenyl carbonate, a compound of high industrial relevance for its use in the production of polycarbonates, were determined from T = 302 K to 332 K (0.02–1 Pa).     

Vapor–liquid equilibrium of fatty acid ethyl esters determined using DSC

The vapor–liquid equilibrium data for the systems: ethyl palmitate + ethyl stearate at 5332.9 Pa, ethyl palmitate + ethyl oleate at 5332.9 Pa and 9332.6 Pa and ethyl palmitate + ethyl linoleate at 9332.6 Pa were determined by differential scanning calorimetry (DSC). The esters used in this study are the major components of biodiesel obtained from the transesterification of soybean oil with ethanol. According to the results, DSC is appropriate for determining the vapor–liquid equilibrium of binary systems. The binary interaction parameters of the models Wilson, NRTL and UNIQUAC were fitted to the experimental data obtained in this study.     

Speed of sound,density, and heat capacity for (2-methyl-2-butanol + heptane) at pressures up to 100 MPa and temperatures from (293 to 318) K. Experimental results and theoretical investigations

In this paper, some new physicochemical properties of (2-methyl-2-butanol + heptane) are investigated using an acoustic method. Of clear interest to us is the study of the effect of branched structure of alcohol on association in mixtures with heptane and consequently, the effect of temperature and pressure on deviations from ideal solution behaviour. Thus, this work presents experimental properties and theoretical study of (2-methyl-2-butanol + heptane) as functions of temperature and pressure over the entire composition range. The densities and speeds of sound in (2-methyl-2-butanol + heptane) have been measured for temperatures ranging from (293 to 318) K under atmospheric pressure and under elevated pressures up to 101 MPa, respectively. The densities, heat capacities and appropriate excesses of these binaries were calculated for the same temperatures and for pressures up to 100 MPa. The acoustic method was applied in the calculations. The effects of pressure and temperature on the excess molar volume and the excess molar heat capacity of (2-methyl-2-butanol + heptane) are explained in terms of the influence of the molecular size and configuration of the alcohols on their self-association capability, packing effect, and the non-specific interactions between the 2-methyl-2-butanol and heptane basing on the results obtained from the modified ERAS model.     

Recommended sublimation pressure and enthalpy of benzene

Recommended vapor pressures of solid benzene (CAS Registry Number: 71-43-2) which are consistent with thermodynamically related crystalline and ideal-gas heat capacities as well as with properties of the liquid phase at the triple point temperature (vapor pressure, enthalpy of vaporization) were established. The recommended data were developed by a multi-property simultaneous correlation of vapor pressures and related thermal data. Vapor pressures measured in this work using the static method in the temperature range from 233 K to 260 K, covering pressure range from 99 Pa to 1230 Pa, were included in the simultaneous correlation. The enthalpy of sublimation was established with uncertainty significantly lower than the previously recommended values.     

Femtosecond degenerate four-wave-mixing measurements of coherent intramolecular vibrations in an ultrafast electron transfer system

Femtosecond degenerate four-wave-mixing (DFWM) spectroscopy was carried out to investigate the behavior of coherent wavepacket motion in an ultrafast intermolecular electron transfer (ET) system which consists of a dye molecule, oxazine 1 (Ox1), in an electron donating solvent, N,N-dimethylaniline (DMA). Due to the ultrafast ET in DMA with time constant of ca. 59–81 fs, acceleration of the vibrational dephasing for the excited state mode at 562 cm⁻¹ was observed by the DFWM measurement and confirmed by pump-probe (PP) spectroscopy. Interestingly, the dephasing time of the excited state mode in DMA is in the order of 160–240 fs, which is significantly longer than the time constant of ET, which indicates that the oscillation is not diminished instantaneously by the ET but somewhat persists into the product state.     

Vapour pressures of n-hexane determined by comparative ebulliometry

The vapour pressures of n-hexane have been measured using comparative ebulliometry with water as the reference fluid. The measurements cover the temperature and pressure range (315.7 K, 41.1 kPa) to (504.0 K, 2876.8 kPa) and join smoothly with results selected from the literature to provide consistent results down to (289.7 K, 13.8 kPa). The combined data set have been described by a Wagner style equation with a fractional standard deviation of 4.2 · 10⁻⁵ in the vapour pressure. The critical pressure p_c was treated as an adjustable parameter and the value of p_c = 3027 kPa was calculated from the smoothing equation using a selected critical temperature of T_c = 507.49 K. The calculated normal boiling temperature is T_b = 341.866 K and an extrapolation to the triple-point temperature T_tp = 177.87 K predicts a triple-point pressure of p_tp = 1.23 Pa.     

Vapour pressure of diethyl phthalate

Measurements of vapour pressure in the liquid phase and of enthalpy of vaporisation and results of calculation of ideal-gas properties for diethyl phthalate are reported. The method of comparative ebulliometry, the static method, and the Knudsen mass-loss effusion method were employed to determine the vapour pressure. A Calvet-type differential microcalorimeter was used to measure the enthalpy of vaporisation. Simultaneous correlation of vapour pressure, of enthalpy of vaporisation and of difference in heat capacities of ideal gas and liquid/solid phases was used to generate parameters of the Cox equation that cover both the (vapour + solid) equilibrium (approximate temperature range from 220 K to 270 K) and (vapour + liquid) equilibrium (from 270 K to 520 K). Vapour pressure and enthalpy of vaporisation derived from the fit are reported at the triple-point temperature T = 269.92 K (p = 0.0029 Pa, Δ_vapH_m = 85.10 kJ · mol⁻¹ ), at T = 298.15 K (p = 0.099 Pa, Δ_vapH_m = 82.09 kJ · mol⁻¹), and at the normal boiling temperature T = 570.50 K (Δ_vapH_m = 56.49 kJ · mol⁻¹). Measured vapour pressures and measured and calculated enthalpies of vaporisation are compared with literature data.     

pH effects on the rate of heterogeneous electron transfer across a fluorine doped tin oxide/monolayer interface

Spontaneously adsorbed monolayers of [Ru(bpy)₂PIC](PF₆)₂ have been formed on fluorine doped tin oxide macro- and microelectrodes, bpy is 2,2′-bipyridyl and PIC is 2-(4-carboxyphenyl)imidazo[4,5-f][1,10]phenanthroline. These monolayers exhibit well-defined, almost ideal electrochemical responses over a wide range of voltammetric scan rates. The formal potential of the Ru^2+/3+ process shifts by less than 30 mV upon immobilization suggesting that the monolayers are well solvated. Significantly, chronoamperometry, conducted on a microsecond timescale, reveals that protonation of the PIC bridging ligand modulates the rate of interfacial electron transfer. The heterogeneous electron transfer rate constant, measured at an overpotential of +50 mV, decreases from 7.0 ± 1.1 × 10⁵ to 0.7 ± 0.1 × 10⁵ s⁻¹ as the pH of the supporting electrolyte is increased from 1.7 to 9.3. These observations are consistent with the redox mechanism occurring via a heterogeneous electron transfer process, the rate of PIC which depends on the energy difference between the metal dπ-orbitals and the lowest unoccupied molecular orbital (LUMO) of the bridge. Protonation of the bridging ligand decreases this energy gap, resulting in an overall increase in the rate of the redox reaction. Significantly, despite the close proximity of the luminophores to a conducting surface, the monolayers remain luminescent suggesting that the electronically excited state is only weakly coupled to the electrode surface. This is consistent with bipyridyl as the site of the excited state in the metal complex.     

Vapor pressures and vaporization enthalpy of codlemone by correlation gas chromatography

The vapor pressure and vaporization enthalpy of codlemone (trans, trans 8,10-dodecadien-1-ol), the female sex hormone of the codling moth is evaluated by correlation gas chromatography using a series of saturated primary alcohols as standards. A vaporization enthalpy of (92.3 ± 2.6) kJ · mol⁻¹ and a vapor pressure, p/Pa = (0.083 ± 0.012) were evaluated at T = 298.15 K. An equation for the evaluation of vapor pressure from ambient temperature to boiling has been derived by correlation for codlemone. The calculated boiling temperature of T_B = 389 K at p = 267 Pa is within the temperature range reported in the literature. A normal boiling temperature of T_B = (549.1 ± 0.1) K is also estimated by extrapolation.     

Measurement of the (pressure,density, temperature) relation of a (methane + nitrogen) gaseous mixture using an accurate single-sinker densimeter

A single-sinker magnetic suspension densimeter based on Archimedes’ buoyancy principle is described. Density measurements on high-purity nitrogen demonstrate the performance of the densimeter. Comprehensive (p, ρ, T) measurements at low densities on a gaseous mixture with mole fraction of (0.8977CH₄ + 0.1023N₂) were carried out on this densimeter at six temperatures from (170.586 to 270.054) K and at pressures ranging from (0.1333 to 1.5945) MPa. The overall uncertainty in density is estimated to be 0.1%. The uncertainty in temperature is estimated to be 5 mK and that in pressure is 250 Pa for (0 to 1.5) MPa and 390 Pa for (1.5 to 3) MPa, respectively. The experimental results of the (methane + nitrogen) mixture were compared with REFPROP 9.0, which used GERG-2008 and AGA8 equations of state to predict thermophysical properties of natural gas. The absolute relative deviations of density measurements are all within 0.1%. Meanwhile the experimental results were correlated using the virial equation of state (Virial EOS) with three different mixing rules. The calculated results using the virial EOS combined with VDW mixing rule show good agreement with the experimental data.     

A time-dependent wave packet study of the H4 four-center reaction

A quantum model based on the time-dependent initial state selected wave packet approach was developed to study the four-center (4C) reaction, A₂ + B₂ → 2AB, and the competing collision induced dissociation (CID), A₂ + B₂ → A + B₂ + A, as applied to the H₂(v₁) + H₂(v₂) system important in combustion. A reduced three-dimensional model of the reaction with the atoms constrained to an isosceles trapezium and a realistic global potential energy surface of Aguado et al. [J. Chem. Phys. 101 (1994) 2742], following Hernández and Clary [J. Chem. Phys. 104 (1996) 8413], was used. A method to analyse the reaction flux for 4C and CID reaction probabilities is presented. The initial A₂ vibrational excitation is not only more efficient than translational energy in facilitating the 4C and CID processes, it also reduces the threshold energy. Both the 4C and CID processes exhibit similar threshold energy behavior. For low vibrational excitation in the A₂ diatom, the 4C process is dominant; as the A₂ diatom becomes highly excited the CID process becomes more important at low collision energies with B₂, but as the collision energy increases the 4C process is favored again.     

Laccase–gold nanoparticle assisted bioelectrocatalytic reduction of oxygen

It was found that homogeneous activity of Trametes hirsuta laccase is considerably diminished in the presence of gold nanoparticles (Au-NPs). Heterogeneous electron transfer studies revealed that Au-NPs facilitate direct electron transfer (DET) between the T1 copper site of the laccase and the surface of Au-NP modified electrodes. DET was characterized by the standard heterogeneous ET constant of 0.5 ± 0.6 s^?1 at Au-NPs with an average diameter of 50 nm. As a consequence of this a well pronounced DET based bioelectrocatalytic oxygen reduction with current densities of 5–30 µA cm^?2 has been achieved at the laccase–Au-NP modified electrodes.     

Kinetics of copper UPD on stepped platinum single crystals in the presence of acetonitrile

The kinetics of copper underpotential deposition on stepped Pt(h k l) electrodes with controlled width of (1 1 1) terraces in acidic solutions of copper sulfate with 0–200 mM of acetonitrile (AcN) has been studied by means of cyclic voltammetry. In the presence of AcN Cu UPD process is hindered both at (1 0 0) steps and (1 1 1) terraces of Pt(17 15 15) and Pt(7 5 5) faces due to blocking of the electrode surface with organic molecules, strongly adsorbed at the steps and nearby ones. The decoration of (1 1 0) steps with copper adatoms is slightly accelerated for Pt(7 7 5) electrode in the solution with 0.04 mM AcN. Increase in AcN concentration leads to inhibition of the UPD process. The difference in behavior of the stepped platinum electrodes is controlled by competitive adsorption of AcN, (bi)sulfate and Cu atoms at the step sites. AcN adsorption at (1 0 0) steps is stronger as compared with (1 1 0) ones.     

Removal of suspended clay from water using transmembrane pressure pulsed microfiltration

Transmembrane pressure pulsing (TPP) uses the frequent and periodic reversal of the transmembrane pressure to reduce flux resistances due to membrane fouling. This study examined the effect of TPP on the microfiltration of simulated drinking water (hydrated aluminum silicate solution). Solutions of kaolin clay (0.1–4.0 μm particles, at an approximate concentration of 500 mg l⁻¹ and a turbidity of 402±17 NTU, 0.5 mM CaCl, 2.0 mM NaHCO₃, pH 7.5–7.8) were microfiltered with polyethersulfone (PES) 0.16 μm microfiltration membranes at an operating pressure of 30 kPa. Crossflow shear rates were varied between 165 and 1490 s⁻¹. Pulse frequency was varied between 0.3×10⁻² and 2 Hz, and pulse amplitude was varied between −3 and −16.5 kPa. It was found that the crossflow shear rates did not significantly effect the non-pulsed permeate flux. An optimum pulse amplitude of about 10 kPa was necessary to maximize the permeate flux for pulse frequencies between 0.3×10⁻² and 2.0 Hz. To insure a reduced solute flux, pulse frequencies less than 0.1 Hz were required. These results indicate that TPP can significantly reduce membrane fouling by inorganic particulate materials that are potentially important constituents of natural waters without negatively impacting the rejection of sub-micron particles due to interactions with material accumulated on the membrane.     

Dew points of binary carbon dioxide + water and ternary carbon dioxide + water + methanol mixtures: Measurement and modelling

Dew points for four carbon dioxide + water mixtures between 1.2×10⁵ and 41.1×10⁵ Pa in the temperature range from 251.9 to 288.2 K, and eight carbon dioxide + water + methanol mixtures between 1.2×10⁵ and 43.5×10⁵ Pa and temperatures from 246.0 to 289.0 K were experimentally determined. The experimental results obtained on the binary and ternary systems were analysed in terms of a predictive excess function–equation of state (EF–EOS) method, which reproduced the experimental dew point temperature data with absolute average deviation (AAD) between 0.8 and 1.8 K for the systems with water, and from 0.0 to 2.7 K for the systems with water and methanol. The experimental results obtained for carbon dioxide + water mixtures, with molar fraction of water lower than 0.00174, at pressure values higher than 5×10⁵ Pa were also compared to a predictive equation of state model. It reproduced experimental dew point temperature data with AAD between 0.2 and 0.6 K.     

Hollow fiber supported liquid membrane microextraction of Cu2+ followed by flame atomic absorption spectroscopy determination

Hollow fiber supported liquid membrane microextraction, a relatively new sample preparation technique, has attracted much interest in the field of environmental analysis. In the current study, a novel method based on hollow-fiber liquid-phase microextraction and flame atomic absorption spectrometry (FAAS) for the measurement of copper ion in aqueous samples is described. Hollow-fiber liquid-phase microextraction conditions such as the type of extraction solvent, pH, the stirring rate, and the amounts of chelating agents, sample volume, and the extraction time were investigated. Under the optimized conditions, the linear range was found to be 0.01–15 μg ml^?1 for copper ion, and the limit of detection to be 0.004 μg ml^?1. Tap water and surface water samples collected from Mashhad, Iran and Dorongar river; Khorasan, Iran, respectively, were successfully analyzed using the proposed method. The recoveries from the spiked water samples were 72.4% and 105%, respectively; and the relative standard deviation (RSD) at the 2 μg ml^?1 level was 6%.     

Dealing with interference challenge in the electrochemical detection of As(III) —A complexometric masking approach

Copper ion has been reported to be a major interference in the electrochemical detection of arsenic (III) ion in water. Therefore the development of a simple approach to alleviate this interference challenge is important. We present the use of ammonia solution as a masking agent for Cu(II) interference in the square wave anodic stripping voltammetry of As(III) on a gold nanoparticle modified glassy carbon electrode (GCE). AuNPs were electrochemically deposited by cyclic voltammetry on a GCE from a potential range of − 400 mV to 1100 mV for 10 cycles. Square wave anodic stripping voltammetry (SWASV) was used to detect As(III) in water with and without Cu(II) based on the following optimised conditions: pH = 3, deposition potential = − 600 mV, and deposition time = 60 s. Ammonia solution was added to the analyte solution and the effect on mitigating copper interference was studied. The presence of ammonia complexed the Cu(II) ion thereby excluding Cu(II) from interfering with the As(III) signal.     

Triangular silver nanoplates: Properties and ultrasensitive detection of miRNA

Triangular silver nanoplates (TSNPs) have been functionalised with probe strand miRNA that is complementary in part to the target nucleic acid, miR-132-3p, that is associated with neuroblastoma. These TSNPs were immobilised in gold microcavities via complementary miRNA hybridisation and can give plasmonic enhancement of the Raman response. Optimum enhancement can be achieved by using different excitation wavelengths and changing the distance between the nanoplate and the surface of the cavity. As silver is electrocatalytically active to the reduction of hydrogen peroxide, these probe-functionalised TSNPs can be used in a miRNA assay where a linear response was obtained for target concentrations from 100 fM to 1 μM target concentration, with a current generated of 100 μA.     

Efficient passivation of SnO2 nano crystallites by Indoline D-149 via dual chelation

For the first time in SnO₂ based dye solar cells, here we report, efficiency exceeding 3% of the cells consisting with Indoline D-149 dye with unmodified SnO₂ nano-crystallites. The cells sensitized with metal free D-149 dye together with liquid electrolyte comprising with 0.5 M tetrapropyl ammonium iodide and 0.05 M iodine in a mixture of acetonitrile and ethylene carbonate (1:4 by volume) delivered a short circuit current density of 10.4 mA cm^?2 with an open circuit voltage of 530 mV under the illumination of 100 mW cm^?2 (AM1.5) having an efficiency of 3.1%. As evident from the FTIR measurement, strong surface passivation of recombination centers of SnO₂ crystallites due to the dual mode of attachment of dye molecules to the surface of SnO₂ via both COOH and S–O direct bond might be the possible reason for this enhancement in these SnO₂ based cells.