Henry’s law constant for environmentally significant compounds

Many nonvolatile organic compounds, e.g., polyaromatic hydrocarbons (PAHs), are readily stripped during aerobic biodegradation. This is because of the high infinite dilution activity coefficient resulting from forces generated by the water-organic interactions at the molecular level. Several models have been proposed for air-stripping based on the Henry’s law constant. By definition, the Henry’s law constant is the infinite dilution activity coefficient multiplied by the pure component vapor pressure. In this article, a gas saturation technique was used to measure the very low vapor pressures exhibited by these nonvolatile compounds. Literature values of other PAHs have been tabulated and are presented. For determining infinite dilution activity coefficients, a differential ebulliometery apparatus has been constructed. In this technique, the boiling point difference between pure water and a water-organic solution is measured very precisely. Thermodynamics is then used to calculate the infinite dilution activity coefficient. The method’s accuracy has been tested using the phenol-water system.     

Development of a Henry’s constant correlation and solubility measurements of n-pentane,i-pentane,cyclopentane, n-hexane,and toluene in water

In this communication, we report new experimental data on n-pentane, i-pentane, cyclopentane, n-hexane, and toluene solubility in water at low temperature (below 298.15 K) and atmospheric pressure conditions. The new experimental data together with those reported in the literature have been used in developing a new equation for Henry’s constants of normal alkanes (methane to decane), BETEX compounds, and acid gases in aqueous phase over a wide range of temperature (typically from 273.15 K to 373.15 K). The new equation is based on a thermodynamic model, which uses the Peng–Robinson equation of state combined with the classical quadratic mixing rules for modelling non-aqueous phases, while the NRTL model is used to calculate the water activity.The predictions of the developed thermodynamic model are compared to the experimental data and the results of a thermodynamic approach, which uses the Valderrama modification of the Patel–Teja equation of state and non-density dependent mixing rules for modelling all fluid phases. Good agreement is observed between the experimental data and the model predictions.     

Determination of Henry’s constant using a photoacoustic sensor

We present a simple method for measuring Henry’s constant k_Hof ethanol using photoacoustic spectroscopy. At T =  298.1 K the measured value fork_H is (0.877  ±  0.039)kPa · kg · mol ^− 1. Our data show that Henry’s law is valid at ethanol molalities between 0.1mol · kg ^− 1 and 1.4 mol · kg ^− 1. The temperature dependence of Henry’s constant was carefully examined by measuring the ethanol vapour pressure of six different aqueous solutions between T =  273.1 K and T =  298.1 K. By analysing the gas phase concentration and applying Henry’s law, an ethanol molality of 0.864 mol · kg ^− 1in the liquid phase can be measured with an error of  ± 0.038mol · kg ^− 1. The detection limit of the photoacoustic sensor is a gaseous ethanol pressure of 10 ^− 3kPa. Ethanol molality changes as low as 1.10 ^− 3mol · kg ^− 1can be measured.     

Determination of the emanation coefficient and the Henry’s law constant for the groundwater radon

The radon emanation coefficient (ε) from aquifer rock and the Henry’s law constant (H) of radon were determined by measuring activity concentrations using liquid scintillation counter (LSC). For the evaluation of the method, the coefficients were measured at 0, 10 and 20 °C and the temperature dependency of the coefficients was compared with others. The radon emanation coefficients from the rock particles used in this work are 0.0845, 0.1007 and 0.1308 at 0, 10 and 20 °C, respectively. The dimensionless Henry’s law constants for the groundwater used in this work are 0.994, 1.153 and 2.641 at 0, 10 and 20 °C, respectively. The results show a good agreement with those in literatures.     

A “phantom bubble” model for the distribution of free volume in polymers

A new approach to investigate free volume in atomistic simulation was devised. The atoms in the structure are represented by hard spheres. A phantom bubble is defined as an empty sphere, which contacts four or more hard spheres of atoms simultaneously in 3 dimensional space and does not overlap with any atom in the structure. Phantom bubbles are only allowed to overlap with other phantom bubbles. For the purpose of illustration, phantom bubbles were constructed in a fully atomistic structure. An amorphous polyethylene was prepared in a periodic box having the dimension of 28.2×28.2×28.2 Å at 293 K and a density of 0.83 g/cm³. There were two fully atomistic polymeric chains (each C₄₀₀H₈₀₂) in the box. All the atoms in the system were assumed to be hard spheres, usually with 89% of their van der Waals radii. Larger and smaller radii were also considered. The size distribution of phantom bubbles in this system was calculated and the bubbles had a median radius of 0.8 Å. Small changes in the radii used for the atoms have little effect on the shape of the distribution function.     

Evaluation of a generalized regression artificial neural network for extending cadmium’s working calibration range in graphite furnace atomic absorption spectrometry

A generalized regression artificial neural network (GRANN) was developed and evaluated for modeling cadmiums nonlinear calibration curve in order to extend its upper concentration limit from 4.0 g L^–1 up to 22.0 g L^–1. This type of neural network presents important advantages over the more popular backpropagation counterpart which are worth exploiting in analytical applications, namely, (1) a smaller number of variables have to be optimized, with the subsequent reduction in development hassle; and, (2) shorter development times, thanks to the fact that the adjustment of the weights (the artificial synapses) is a non-iterative, one-pass process. A backpropagation artificial neural network (BPANN), a second-order polynomial, and some less frequently employed polynomial and exponential functions (e.g., Gaussian, Lorentzian, and Boltzmann), were also evaluated for comparison purposes. The quality of the fit of the various models, assessed by calculating the root mean square of the percentage deviations, was as follows: GRANN > Boltzmann > second-order polynomial > BPANN > Gauss > Lorentz. The accuracy and precision of the models were further estimated through the determination of cadmium in the certified reference material Trace Metals in Drinking Water (High Purity Standards, Lot No. 490915), which has a cadmium certified concentration (12.00±0.06 g L^–1) that lies in the nonlinear regime of the calibration curve. Only the models generated by the GRANN and BPANN accurately predicted the concentrations of a series of solutions, prepared by serial dilution of the CRM, with cadmium concentrations below and above the maximum linear calibration limit (4.0 g L^–1). Extension of the working range by using the proposed methodology represents an attractive alternative from the analytical point of view, since it results in less specimen manipulation and consequently reduced contamination risks without compromising either the accuracy or the precision of the analyses. The implementation of artificial neural networks also helps to reduce the trial-and-error task of looking for the right mathematical model from among the many possibilities currently available in the various scientific and statistic software packages.     

Paneth’s epistemology of chemical elements in light of Kant’s Opus postumum

Friedrich Paneth’s conception of “chemical element” has functioned as the official definition adopted by the International Union of Pure and Applied Chemistry since 1923. Paneth maintains a distinction between empirical and “transcendental” concepts of element; furthermore, chemical science requires fluctuation between the two. The origin of the empirical-transcendental split is found in Immanuel Kant’s classic Critique of Pure Reason (1781/1787). The present paper examines Paneth’s foundational concept of element in light of Kant’s attempt, late in life, to revoke key distinctions made in his Critique, including that of regulative and constitutive functions of reason. In a section of his Opus postumum devoted to the “Transition from the Metaphysical Foundations of Natural Science to Physics,” Kant bends his philosophical system to address the newly emerging sciences of matter of his time. Specifically, he tried, without success, to develop the transcendental ground for microscale motions of bodies encountered in physical, electrical and chemical processes. Paneth’s discussion of chemical element does not take the Opus postumum into account, which is why it begins with a rejection of Kant’s rejection (in his earlier writings) of chemistry’s status as science. I make the case that Paneth’s definition of element effectively maintains something very like Kant’s critical separation of regulative and constitutive principles, while a advancing the concept of chemical science.     

A simple modification of the Flory—Huggins theory for polymers in non-polar or slightly polar solvents

Starting from the concept of free volume dissimilarity, a simple modification of the non-combinatorial part of the Flory—Huggins equation is proposed. According to this modification, a new relation is derived to calculate the activity of a solvent in mixture with a polymer. It contains two empirical parameters, whose values can be determined by regressing binary vapour—liquid experimental data. The proposed equation has been applied to several binary systems which can be grouped in three classes of mixtures: non-polar/non-polar, non-polar/polar and polar/polar. Satisfactory results have been obtained in the case of non-polar or slightly polar mixtures, however, for strongly polar systems, the new equation is inadequate. The proposed modification of the Flory—Huggins theory is particularly suitable for engineering calculations.     

Molecular interpretation of Trouton’s and Hildebrand’s rules for the entropy of vaporization of a liquid

The entropy of vaporization at a liquid’s boiling point is well approximated by Trouton’s rule and even more accurately by Hildebrand’s rule. A cell method is used here to calculate the entropy of vaporization for a range of liquids by subtracting the entropy of the gas from that of the liquid. The liquid’s entropy is calculated from the force magnitudes measured in a molecular dynamics simulation based on the harmonic approximation. The change in rotational entropy is not accounted for except in the case of liquid water. The predicted entropies of vaporization agree well with experiment and Trouton’s and Hildebrand’s rules for most liquids and for water except other liquids with hydrogen bonds. This supports the idea that molecular rotation is close to ideal at a liquid’s boiling point if hydrogen bonds are absent; if they are present, then the rotational entropy gain must be included. The method provides a molecular interpretation of those rules by providing an equation in terms of a molecule’s free volume in a liquid which depends on the force magnitudes. Free volumes at each liquid’s boiling point are calculated to be ～1 Å³ for liquids lacking hydrogen bonds, lower at ～0.3 Å³ for those with hydrogen bonds, and they decrease weakly with increasing molecular size.     

Features of the adsorption of aryl- and hetaryl-substituted 1,3,4-oxadiazoles from solutions on the surface of porous graphitic carbon in Henry’s range

Adsorption in Henry’s range of structurally related aryl- and hetaryl-substituted 1,3,4-oxadiazoles from n-hexane-dichloromethane and water-acetonitrile solutions on the surface of porous graphitic carbon (PGC) under the conditions close to equilibrium is studied by high-performance liquid chromatography. The characteristics of sorption of 1,3,4-oxadiazoles from solutions on the surface of this adsorbent, octadecyl silica gel, and on hypercrosslinked polystyrene are compared. It is shown that the structure of the molecules and their Van der Waals surface area and polarity affect adsorption on a PGC surface. A variant of the mechanism of adsorption of the polar molecules on the PGC surface, explaining the anomalously high values of their Henry constants of adsorption and based on the planar location of the 1,3,4-oxadiazoles molecules with respect to the adsorbent surface and the specific adsorbate-adsorbent intermolecular interaction in addition to the background dispersion interactions, is proposed. It is established that the linear the Gibbs energy relationship upon the adsorption of the studied compounds from n-hexane-dichloromethane and water-acetonitrile solutions on the PGC surface holds.     

A skeptic’s review of the New SI

Proposals in draft form have been circulated for new Système International (SI) measurement units that are expected to be official instruments of the Treaty of the Metre by 2015. This review outlines the substance of the proposals and examines some of the consequences of the continuing evolution of the SI toward inter-dependence of base units and quantities since its introduction in 1960. The proposals in question fix at an exact value a number of inter-related fundamental natural constants such as the speed of light, the Planck constant, the elementary charge and Boltzmann’s constant. All SI units are then so defined that their magnitude is set by those fixed values. Notably, the ongoing confusions about chemical measurements and the thermodynamic ‘mole’ are exacerbated. On the big principles of the basic purpose of the SI to facilitate communication and the fixing of fundamental physical constants of nature, there are significant problems and unanswered questions. They risk: damage to the enterprise of science; wide economic loss including increased transaction costs and barriers to global trade; barriers to new technologies and to improvements in measurement accuracy; loss of measurement compatibility or consistency; and a circular global measurement system vulnerable to undetectable systematic errors with serious adverse consequences for environmental decision making among many other vital human activities. The New SI requires frank and open discussion throughout science, technology, industry, trade, and global policy well before irreversible decisions are made.     

OH frequency shifts of fluorinated alcohols in nonpolar solvents for high pressures and low temperatures

Infrared spectra of fluorinated alcohols in nonpolar solvents were discussed in dependence on high pressures and low temperatures. The frequency of the monomeric OH stretching vibration, measured for the temperature at 20°C and for the pressure at 100 kPa, is about 20 cm⁻¹ lower than in the gas phase. The frequency decreases with increasing pressure up to 2 GPa. The frequency shift turns round for a further pressure increase. For higher than 8 GPa pressures the frequency is blue shifted in comparison to the gaseous state. The OH frequency decreases for a temperature change from 400 K up to 100 K. The frequency shift turns round for lower temperatures. This finding will be explained by a superposition of the unperturbed OH potential with Lennard-Jones function for different distances.     

Synthesis of aromatic polyamidines in Eaton’s reagent

Aromatic polyamidines are prepared via the polycondensation of dicarboxamides and diamines in Eaton’s reagent. The polymers are investigated by elemental analysis and IR and NMR spectroscopy. Polyamidines are well soluble in concentrated sulfuric acid and concentrated formic acid and in polar organic solvents, and temperatures corresponding to their 10% weight losses are in the range 245–280°C.