Isobaric vapor-liquid equilibrium for binary systems containing benzothiophene

Isobaric vapor-liquid equilibrium (VLE) of the following systems was measured with a recirculation still: benzothiophene + dodecane at 99.6 kPa, benzothiophene + 1-dodecene at 100.1 kPa, and benzothiophene + 1-octanol at 100 kPa. All systems studied exhibit positive deviation from Raoult's law. A minimum temperature azeotrope was found in the systems benzothiophene + dodecane (x₁ = 0.491, P = 99.6 kPa, T = 484.72 K) and benzothiophene + 1-dodecene (x₁ = 0.185, P = 100.1 kPa, T = 484.45 K). No azeotropic behavior was found in benzothiophene + 1-octanol system at 100 kPa. The experimental results were correlated with the Wilson model and compared to COSMO-SAC predictive model. Liquid and vapor phase compositions were determined with gas chromatography. All measured data sets passed the thermodynamic consistency tests. The activity coefficients at infinite dilution are also presented.     

Phase equilibria on binary systems containing diethyl sulfide

Isothermal vapor-liquid equilibrium (VLE) of the following systems was measured with a recirculation still: diethyl sulfide + ethanol at 343.15 K, diethyl sulfide + 1-propanol at 358.15 K, and diethyl sulfide + propyl acetate at 363.15 K. Diethyl sulfide + ethanol at 343.15 K and diethyl sulfide + 1-propanol at 358.15 K systems exhibit positive deviation from Raoult's law, whereas diethyl sulfide + propyl acetate at 363.15 K system exhibits only slight positive deviation from Raoult's law. A maximum pressure azeotrope was found in the systems diethyl sulfide + ethanol (x₁ = 0.372, P = 88.4 kPa, T = 343.15 K) and diethyl sulfide + 1-propanol (x₁ = 0.640, P = 96.8 kPa, T = 358.15 K). No azeotropic behavior was found in diethyl sulfide + propyl acetate system at 363.15 K. The experimental results were correlated with the Wilson model and compared to COSMO-SAC predictive model. Liquid and vapor phase compositions were determined with gas chromatography. All measured data sets passed the thermodynamic consistency tests. The activity coefficients at infinite dilution are also presented.     

Ag adsorption on Cd-terminated CdS (0 0 0 1) and S-terminated CdS (0 0 0 1?) surfaces: First-principles investigations

First-principles calculations are performed to study the adsorption of Ag at Cd-terminated CdS (0 0 0 1) and S-terminated CdS (0 0 0 1?) surfaces as a function of Ag coverage. Our results reveal that Ag adsorption at Cd-terminated (0 0 0 1) has a large binging energy than at S-terminated (0 0 0 1?) surface. For Ag adsorption at Cd-terminated (0 0 0 1) surface, T4 structure is more favorable and the Ag-Cd bond posses an ionic-like character. While for Ag adsorption at S-terminated (0 0 0 1?) surface, the H3 structure is most stable and the bonding between Ag-S is covalent. It is found that the magnitude and the sign of surface dipole moment are partly determined by the difference between the electronegativities of Ag and the host atom bonding with Ag. The adsorption energy changes as a function of Ag coverage. In addition, related properties of Ag cluster adsorption at Cd-terminated (0 0 0 1) surface are also discussed.     

Phase equilibria on five binary systems containing 1-butanethiol and 3-methylthiophene in hydrocarbons

Isothermal vapor–liquid equilibrium (VLE) of the following systems was measured with a recirculation still: 1-butanethiol + methylcyclopentane at 343.15 K, 1-butanethiol + 2,2,4-trimethylpentane at 368.15 K, 3-methylthiophene + toluene at 383.15 K, 3-methylthiophene + o-xylene at 383.15 K, and 3-methylthiophene + 1,2,4-trimethylbenzene at 383.15 K. 1-Butanethiol + methylcyclopentane and 1-butanethiol + 2,2,4-trimethylpentane systems exhibit positive deviation from Raoult's law, whereas systems containing 3-methylthiophene in aromatic hydrocarbons exhibit only slight positive deviation from Raoult's law. A maximum pressure azeotrope was found in the system 1-butanethiol + 2,2,4-trimethylpentane (x₁ = 0.548, P = 100.65 kPa, T = 368.15 K). The experimental results were correlated with the Wilson model and compared with original UNIFAC and COSMO-SAC predictive models. Raoult's law can be used to describe the behavior of 3-methylthiophene in aromatic hydrocarbons at the experimental conditions in this work. Liquid and vapor-phase composition were determined with gas chromatography. All measured data sets passed the thermodynamic consistency tests applied. The activity coefficients at infinite dilution are also presented.     

Reaction between carbon dioxide and elementary fluorine

Reactions between carbon dioxide and fluorine were examined at temperatures of 303-523 K under various pressure and mixture ratios of both gases. Reactions were carried out similarly under the existence of NaF, CsF and EuF₃.After the reaction, fluorine was removed and the reaction products were analyzed using FT-IR, GC/FT-IR and GC/MS. The major products were CF₃OF, COF₂, CF₄ and CF₂(OF)₂.The best yield of COF₂ was 11.1% under the reaction condition of CO₂/F₂ = 76 kPa/76 kPa with temperature of 498 K for 72 h in a direct reaction. The formation rate of COF₂ in the direct reaction was estimated as 0.232 dm³ mol⁻¹ h⁻¹ under the reaction conditions of CO₂/F₂ = 76 kPa/76 kPa, at 498 K. In the presence of CsF, it was estimated as 1.88 dm³ mol⁻¹ h⁻¹ at CO₂/F₂ = 76 kPa/76 kPa at 498 K.The activation energy of the COF₂ formation in the direct reaction was estimated as 45.7 kJ mol⁻¹ at CO₂/F₂ = 76 kPa/76 kPa at 498 K. In addition, 24.2 and 38.9 kJ mol⁻¹ were evaluated at CO₂/F₂ = 76 kPa/76 kPa at 498 K, respectively, in the presence of CsF and EuF₃.     

Liquid-liquid equilibria of ternary mixtures of dimethyl carbonate, diphenyl carbonate, phenol and water at 358.15 K

The ternary liquid-liquid equilibria (LLE) of the following systems were analytically determined at 358.15 K at atmospheric pressure using stirred and thermo-regulated cells: {dimethyl carbonate (DMC) + diphenyl carbonate (DPC) + water}, {DMC + phenol + water} and {DPC + phenol + water}. The experimental ternary LLE data were correlated with the NRTL and UNIQUAC activity coefficient models. Additionally, the Bachman-Brown correlation was used to ascertain the reliability of the experimental data for each system.     

Measurement and calculation of vapor–liquid equilibria for methanol + glycerol and ethanol + glycerol systems at 493–573 K

The vapor–liquid equilibria for methanol + glycerol and ethanol + glycerol systems were measured by a flow method at 493–573 K. The pressure conditions focused in this work were 3.03–11.02 MPa for methanol + glycerol system and 2.27–8.78 MPa for ethanol + glycerol system. The mole fractions of alcohol in vapor phase are close to unity at the pressures below 7.0 MPa for both systems. The pressures of liquid saturated lines of the liquid phase for methanol + glycerol and ethanol + glycerol systems are higher than that for the mixtures containing alcohol and biodiesel compound, methyl laurate or ethyl laurate.     

Vapour–liquid equilibrium for β-myrcene and carbon dioxide and/or hydrogen and the volume expansion of β-myrcene or limonene in CO2 at 323.15 K

Vapour–liquid equilibrium measurements for binary and ternary (carbon dioxide + β-myrcene and carbon dioxide + β-myrcene + hydrogen) systems have been carried out at 323.15 K and pressures in the range from 7 MPa to the critical pressure of the binary mixture and at pressures from 10 to 14 MPa for the investigated ternary systems. Samples from the coexisting phases were taken, and compositions were determined experimentally. Results were correlated using the Peng–Robinson and the Soave–Redlich–Kwong equations of state with the Mathias–Klotz–Prausnitz mixing rule. The set of interaction parameters for the employed equations of state and applied mixing rule for the system of CO₂ + β-myrcene and of CO₂ + β-myrcene + H₂ were obtained. Additionally, the volume expansion of the liquid phase for the binary mixtures (carbon dioxide + β-myrcene and carbon dioxide + limonene) were measured at 323.15 K and at pressures from 4 MPa up to very close to the critical pressure of the mixture. The ratio of liquid phase total volumes at the given pressure and at 4 MPa was calculated.     

Excess molar enthalpies of methylformate + (1-propanol, 2-propanol, 1-butanol, 2-butanol and 1-pentanol) at T = 298.15 K, p = (5.0, 10.0) MPa, and methylformate + 1-propanol at T = 333.15 K, p = 10.0 MPa

A high pressure flow-mixing isothermal calorimeter is used to determine the excess molar enthalpies of methylformate + (1-propanol, 2-propanol, 1-butanol, 2-butanol and 1-pentanol) at T = 298.15 K and p = (5.0, 10.0) MPa, and methylformate + 1-propanol at T = 333.15 K and p = 10.0 MPa. The Redlich-Kister equation is fit to the experimental results.     

De-contamination of pesticide residues in food by ionizing radiation

The role of gamma irradiation on removal of pesticides in aqueous solutions or in vegetables and fruits was investigated. Radiation - induced decontamination of pesticides is generally greater in aqueous solutions than in selected vegetables and fruits. Residues of malathion (0.5 ppm in potatoes, 8 ppm in onions and dates), pirimiphos-methyl (1 ppm in onions and grapes) and cypermethrin (0.05 ppm in potatoes and 0.1 ppm in onions) were not reduced to below maximum residue limits (MRLs) for irradiation doses up to 1 kGy. The same trend was observed when irradiation was performed for grapes fortified with malathion (8 ppm) and cypermethrin (2 ppm) for absorbed doses up to 2 kGy. Ionizing radiation reduced the residues of pirimiphos-methyl (0.05 ppm in potatoes at1 kGy, 1 ppm in grapes at 2 kGy and 0.1 ppm in dates at1 kGy), malathion (8 ppm in grapes at 7 kGy) and cypermethrin (2 ppm in grapes at 7 kGy) to below maximum residue limits (MRLs).     

Direct electrochemistry of hemoglobin and myoglobin at didodecyldimethylammonium bromide-modified powder microelectrode and application for electrochemical detection of nitric oxide

Hemoglobin (Hb) and myoglobin (Mb) were immobilized at the didodecyldimethylammonium bromide (DDAB)-modified powder microelectrode (PME) to fabricate Hb-DDAB-PME and Mb-DDAB-PME. Direct electrochemistry of Hb and Mb were achieved on the DDAB-modified PME. The formal potential was −0.224 V for Hb and −0.212 V for Mb (vs. SCE). The apparent surface concentration of Hb and Mb at the electrode surface was 2.83 × 10⁻⁸ and 9.94 × 10⁻⁸ mol cm⁻². The Hb-DDAB-PME and Mb-DDAB-PME were successfully applied for measurement of NO in vitro. The anodic current peaks for NO oxidation at +0.7 V and the cathodic current peaks for NO reduction at −0.85 V on the CV curves were obtained on the modified electrodes. For detection of NO at +0.7 V, the sensitivity is 3.31 mA μM⁻¹ cm⁻² for Hb-DDAB-PME and 0.6 mA μM⁻¹ cm⁻² for Mb-DDAB-PME. The detection limit is 5 nM for Hb-DDAB-PME and 9 nM for Mb-DDAB-PME. The linear response range is 9-100 and 28-330 nM for Hb- and Mb-modified PME, respectively. For the electrochemical detection of NO at −0.85 V by using Hb-DDAB-PME, the detection sensitivity is 39.56 μA μM⁻¹ cm⁻²; the detection limit is as low as 0.2 μM; and the linear response range is 1.90-28.08 μM.     

Phase equilibria on four binary systems containing 3-methylthiophene

Isothermal vapor–liquid equilibrium (VLE) for 3-methylthiophene + 2,2,4-trimethylpentane at 368.15 K, 3-methylthiophene + 2,4,4-trimethyl-1-pentene at 368.15 K, 3-methylthiophene  + cyclohexane at 348.15 K, and 3-methylthiophene + 1-hexene at 333.15 K were measured with a recirculation still. All systems exhibit positive deviation from ideality. No azeotropic behavior was found in all systems. The experimental results were correlated with the Wilson model and also compared with the original UNIFAC and UNIFAC-Dortmund predictive models. Analyses of liquid and vapor-phase composition were determined with gas chromatography (GC). All VLE measurements passed the used thermodynamic consistency tests (integral, infinite dilution and point test). The activity coefficients at infinite dilution are also presented.     

Development, validation and application of a method based on DI-SPME and GC-MS for determination of pesticides of different chemical groups in surface and groundwater samples

A simple and rapid method based on solid-phase micro extraction (SPME) technique followed by gas chromatography-mass spectrometry with selected ion monitoring (GC-MS, SIM) was developed by the simultaneous determination of 16 pesticides of seven different chemical groups [Six organophosphorus (trichlorfon, diazinon, methyl parathion, malathion, fenthion and ethyon), three pyrethroids (bifenhin, permethrin, cypermethrin), two imidazoles (imazalil and prochloraz), two strobilurins (azoxystrobin and pyraclostrobin), one carbamate (carbofuran), one tetrazine (clofentezine), and one triazole (difenoconazole)] in water. The pesticides extraction was done with direct immersion mode (DI-SPME) of the polyacrilate fiber (PA 85 µm). The extraction temperature was adjusted to 50 °C during 30 min, while stirring at 250 rpm was applied. After extraction, the fiber was introduced in the GC injector for thermal desorption for 5 min. at 280 °C. The method was validated using ultra pure water samples fortified with pesticides at different concentration levels and shows good linearity in the concentrations between 0.05 and 250.00 ng mL^− 1. The LOD and LOQ ranged, from 0.02 to 0.30 ng mL^− 1 and 0.05 to 1.00 ng mL^− 1, respectively. Intra-day and inter-day precisions were determined in two concentration levels (5.00 and 50.00 ng mL^− 1). Intra-day relative standard deviation (%R.S.D.) ranged between 3.6 and 13.6%, and inter-day (%R.S.D.) ranged between 6.3 and 18.5%. Relative recovery tests were carried out spiking the ultra pure sample with standards in three different concentration levels 0.20, 5.00 and 50.00 ng mL^− 1. The recovery at 0.20 ng mL^− 1 level varied from 86.4 ± 9.4% to 108.5 ± 10.5%, at 5.00 ng mL^− 1 level varied from 77.5 ± 10.8% to 104.6 ± 9.6% and at 50.00 ng mL^− 1 level varied from 70.2 ± 4.6% to 98.4 ± 8.5%. The proposed SPME method was applied in twenty-six water samples collected in the “Platô de Neópolis”, State of Sergipe, Brazil. Methyl parathion was detected in five samples with an average concentration of 0.17 ng mL^− 1 and bifenthrin, pyraclostrobin and azoxystrobin residues were found in three samples with average concentrations of 2.28, 3.12 and 0.15 ng mL^− 1, respectively.     

Vapour–liquid equilibrium for the systems diethyl sulphide + 1-butene, +cis-2-butene, +2-methylpropane, +2-methylpropene, +n-butane, +trans-2-butene

Isothermal vapour–liquid equilibrium was measured for the systems of diethyl sulphide + 1-butene, +cis-2-butene, and +2-methylpropene at 312.6 K, diethyl sulphide + n-butane was measured at 317.6 K, diethyl sulphide + trans-2-butene at 317.5 K, and diethyl sulphide + 2-methylpropane at 308.0 K. The pressure–temperature–total composition data were converted into pressure–temperature–liquid–vapour composition data using the method of Barker. Error estimates are provided for each variable. The isothermal parameters for the Wilson, NRTL and UNIQUAC activity coefficient models were regressed. The measurements were compared with the predictions by COSMO segment activity coefficient (COSMO-SAC) and UNIFAC.     

Theoretical studies on the structures and vibrational spectra of Ni, Pd, and Pt phthalocyanines

Electronic structure calculations and spectroscopic assignments for metallophthalocyanines NiPc, PdPc and PtPc are performed on optimized geometries at B3LYP/LANL2DZ level. The order of the sizes of the central hole is computed to be PdPc > PtPc > NiPc, with the hole size of PdPc close to that of PtPc. The Mulliken charges of the central M vary in the order of PtPc > NiPc > PdPc, and the HOMO-LUMO gaps are in the order of NiPc < PdPc < PtPc, in agreement with the experimental result. The simulated IR spectra for the three derivatives are compared with the experimental absorption spectra, and very good consistency has been obtained. The simulated medium intensity bands associated with the metal-ligand vibrations which appear as singlet bands at 880, 877 and 883 cm⁻¹, respectively, exhibit the order of PtPc > NiPc > PdPc, which is the same order as experiment. Furthermore, the metal-ligand vibrational bands for Raman spectra shift in the order NiPc > PtPc > PdPc. The strongest Raman lines predicted at 1562, 1532 and 1534 cm⁻¹ for NiPc, PdPc and PtPc are very sensitive to the metal ion.     

Phase equilibria for systems containing dimethyl disulfide and diethyl disulfide with hydrocarbons at 368.15 K

Isothermal vapor–liquid equilibrium (VLE) for dimethyl disulfide + toluene, dimethyl disulfide + 2,2,4-trimethylpentane, dimethyl disulfide + 2,4,4-trimethyl-1-pentene, and diethyl disulfide + 2,2,4-trimethylpentane at 368.15 K were measured with a recirculation still. All systems exhibit positive deviation from Raoult's law. Dimethyl disulfide + toluene system shows only slight positive deviation from Raoult's law, while dimethyl disulfide + 2,2,4-trimethylpentane, dimethyl disulfide + 2,4,4-trimethyl-1-pentene, and diethyl disulfide + 2,2,4-trimethylpentane systems show larger positive deviation from Raoult's law. Maximum pressure azeotropes were found in systems: dimethyl disulfide + toluene (x₁ = 0.632, P = 66.4 kPa, T = 368.15 K), dimethyl disulfide + 2,2,4-trimethylpentane (x₁ = 0.311, P = 95.8 kPa, T = 368.15 K), and dimethyl disulfide + 2,4,4-trimethyl-1-pentene (x₁ = 0.295, P = 88.4 kPa, T = 368.15 K). No azeotropic behavior was observed in system diethyl disulfide + 2,2,4-trimethylpentane at 368.15 K. The experimental results were correlated with the Wilson model. Original UNIFAC was used to predict dimethyl disulfide + 2,2,4-trimethylpentane and diethyl disulfide + 2,2,4-trimethylpentane systems at 368.15 K. COSMO-SAC predictive model was used to predict infinite dilution activity coefficients for all systems measured. Liquid and vapor-phase composition were determined with gas chromatography. All VLE measurements passed the thermodynamic consistency tests applied. The activity coefficients at infinite dilution are also presented.     

Assessment of hydrate kinetic inhibitors with visual observations

The hydrate inhibition effect of three kinetic inhibitors (inhibex 301, 501, and 713) was assessed from (CH₄ + C₂H₆ + C₃H₈) gas mixture + brine systems using a high pressure sapphire cell. The onset time of hydrate formation was determined by visual observation method and pressure drop profile method, respectively. The experimental results demonstrated that the onset time was able to be determined by the visual observation method all the time while the pressure drop profile method failed to detect the onset time clearly and correctly at lower temperatures. In some cases, the initial appearance of hydrate crystals cannot induce a clear break in the pressure–time relationship curve. The onset time measured by the visual observation method is usually shorter than or at least the same as that determined by the pressure drop profile method. The inhibiting effect on the growth of hydrate crystals can be shown by the difference of the onset time obtained by the two methods. The maximum tolerated subcooling of each inhibitor was also investigated based on the onset time. It was found that inhibex 301 behaves as the best inhibitor that can tolerate the maximum subcooling of 8.3 K at 0.5 wt% and 10.6 K at 1.0 wt%, respectively. The maximum subcooling for inhibex 501 is 6.8 K at 0.5 wt% and 6.6 K at 1.0 wt%, respectively. Inhibex 713 has relatively poor inhibiting effect among the three inhibitors with the maximum subcooling of less than 3.5 K at 0.5 wt% and 5.1 K at 1.0 wt%, respectively.     

Effect of temperature on the performance of proton batteries based on chitosan–NH4NO3–EC membrane

Membranes of chitosan-based proton conductor polymer electrolyte were prepared by dissolving chitosan powder, ammonium nitrate (NH₄NO₃) salt and ethylene carbonate (EC) plasticizer in acetic acid solution. The temperature dependence of the chitosan-based membrane system was found to obey the Arrhenius relationship. The sample with the highest conductance, 18 wt.% CA + 12 wt.% NH₄NO₃ + 70 wt.% EC (CA40N70E), also possesses the lowest activation energy. From linear sweep voltammetry (LSV) results, the membrane is electrochemically stable at a potential of 1.6–1.8 V and a temperature of 298–353 K. The cells were fabricated using zinc powder (Zn) + zinc sulfate heptahydrate (ZnSO₄·7H₂O) + acetylene black (AB) + polytetrafluoroethylene (PTFE)|CA40N70E|manganese (IV) oxide (MnO₂) + AB + PTFE. The open circuit voltages of the cells are decreases as temperature increases, the same trend as that obtained by LSV. The cell performance is excellent at 333 K, with discharge capacity of 42.7 mAh, internal resistance of 16.8 Ω, maximum power density of 14.6 mW cm⁻² and a short-circuit current density of 31.0 mA cm⁻². However, at temperatures above 333 K, decomposition of the membrane degraded the electrochemical properties of the cells.     

The structures,stability, and photoelectron spectroscopy of GaPX (X = C,Si, Ge; O,S; P and Ga) clusters

The equilibrium geometries and vibrational frequencies of GaPX⁻ and GaPX (X = C, Si, Ge; O, S; P and Ga) have been studied by hybrid B3LYP functional at cc-PVTZ and aug-cc-PVTZ levels. The results predict that the most stable structure of GaPC⁻ is linear while the others are trigonal. As for GaPX (X = C, Si, Ge; O, S; P and Ga), the ground structures of GaPC and GaPO are linear while the others are trigonal. The adiabatic electron affinities (AEAs) and vertical detachment energies (VDEs) of GaPX⁻ are calculated at B3LYP/aug-cc-PVTZ level. And the order of the AEAs and VDEs of GaPX⁻ are C < O < Ge ≈ Si < P < S < Ga and C < Ge ≈ Si < P < O < S < Ga, respectively. GaPC exhibits the lowest adiabatic electron affinities of all the clusters studied, indicating a particularly stable neutral species.     

Flow-injection fluorometric quantification of pyruvate using co-immobilized pyruvate decarboxylase and aldehyde dehydrogenase reactor: Application to measurement of acetate, citrate and l-lactate

A flow-injection system for the quantification of pyruvate based on the coupled reactions of pyruvate decarboxylase (PDC) and aldehyde dehydrogenase (AlDH) was conceived and optimized. A co-immobilized PDC and AlDH reactor was introduced into the flow line. Sample and reagent (NAD⁺) were injected into the flow line by an open sandwich method and the increase of NADH produced by the immobilized-enzyme reactor was monitored fluorometrically at 455 nm (excitation at 340 nm). Linear relationships between the responses and concentrations of pyruvate were observed in the ranges of 2.0 × 10⁻⁵ to 1.5 × 10⁻³ M at the flow rate of 1.0 ml min⁻¹ and 5.0 × 10⁻⁶ to 1.0 × 10⁻³ M at the flow rate of 0.5 ml min⁻¹. The relative standard deviation for 10 successive injections was 0.95% at the 1.0 mM level. This FIA system for pyruvate was applied to the measurement of acetate, citrate and l-lactate.