Quantitative accuracy in the gas chromatographic analysis of solvent mixtures

Quantitative accuracy is of great importance in the analysis of bulk mixtures of solvents, particularly when the analysis is related to quality control of very large product volumes like in solvent recovery plants. Serious errors can be made if the effects of density differences between the pure solvents and volume contractions are not properly addressed. In earlier work, the use of an iterative process for correcting such errors has been suggested. However, in the case of volume contractions and mixtures of several solvents, this procedure is difficult to apply. In the present paper, we describe a simple procedure where calibration curves based on mass concentration are utilized. The densities of calibration mixtures of known compositions are determined with a density meter, in order to provide for correction factors caused by volume contractions. Model experiments with mixtures of water, ethanol, acetone and methanol showed a significant improvement in quantitative accuracy. when the suggested calibration strategy was applied.     

Calculation of the vibration–rotational transition intensities of water molecules trapped in an argon matrix: stretching O–H vibrations spectral region

The frequencies and intensities of vibration–rotational transitions of water molecules in an argon matrix were calculated for temperatures of 6 and 30 K. The rigid asymmetric top approximation was used with available literature values of the effective rotational constants in the ground and excited vibrational states. The calculations were carried out by taking into account the existence of a non-equilibrium population distribution between the rotational levels of ortho- and para-water isomers. It was assumed that the temperature relaxation of the population of rotational levels is independent of the ortho- and para-isomers. Comparison of the results of the theoretical calculations with experimental literature data shows good agreement for the majority of the rotational structure lines for symmetric and antisymmetric stretching vibrations both in the frequency values and in the values of the relative intensities.     

Fluorescence emission of excited hydrogen atoms after core excitation of water vapor

The Balmer emission from atomic hydrogen has been recorded across the resonances at the oxygen K edge of the water molecule using synchrotron radiation excitation. The emission is observed to be strongest at excitations to Rydberg resonances. The observations are interpreted using a qualitative model for the dynamics of the core-to-Rydberg excited molecule. The model links the quantum state of the core-excited water molecule via resonant Auger decay and subsequent dissociation to the state of the fluorescing hydrogen atom.     

Ultrafast molecular dissociation of water in ice

Using x-ray emission and photoemission spectroscopies to measure the occupied valence levels in a thin crystalline ice film, we resolve the ionization-induced dissociation of water in ice on a femtosecond time scale. Isotope substitution confirms proton transfer during the core-hole lifetime in spite of the nonresonant excitation. Through ab initio molecular dynamics on the core-ionized state, the dissociation and spectrum evolution are followed at femtosecond intervals. The theoretical simulations confirm the experimental analysis and allow for a detailed study of the dissociative reaction path.     

Elemental composition of fine particulate matter (PM2.5) in Skopje,FYR of Macedonia

Aerosol samples were collected at an urban background site in Skopje, Former Yugoslavic Republic of Macedonia, during four measurement campaigns from December 2006 to October 2007. An impactor was used to collect particulate matter (PM_2.5) aerosol particles and the samples were analyzed for the concentrations of particulate mass, black carbon (BC), and 17 elements. The 12‐h average PM_2.5 concentrations varied in the range 10–140 µg m^?3 with the highest concentrations measured during wintertime pollution episodes and during the summer period. Pair‐wise correlations and crustal enrichment were studied and the data set was analyzed by factor analysis and positive matrix factorization. Major aerosol components were identified as mineral dust (main observed tracers Si, K, Ca, Ti, Fe, Sr, and Rb), combustion (BC, S, K, V, and Ni), traffic‐related aerosol (Pb and Zn), and secondary sulfate combined with mineral dust. Combustion sources dominated during wintertime and were likely due to heavy oil combustion, biomass burning, and other industrial activities within the city area. Mineral dust was observed throughout the year, but the concentrations peaked during the unusually hot and dry summer of 2007. It is concluded that Skopje suffers from serious air pollution due to central and residential heating, the transport sector, and industrial activities within the city, and contributions from mineral dust increase the PM_2.5 concentrations under dry periods. Topography and meteorological conditions aggravate the problems and make the air quality comparable with the conditions in other highly polluted cities in Southern Europe and worldwide. Copyright © 2011 John Wiley & Sons, Ltd.     

On the verification of the applicability of the orthotropic plate wave theory to paper

In the literature one basic work can be found that describes an attempt to verify the applicability of the orthotropic plate wave theory to paper. In the present study we have repeated the key experiment and also modified the original experimental set-up to be able to make new complementary measurements. The performed verification attempt is based on a key experiment in which an ultrasonic resonance method is used. When it is applied to paper, a second resonance can be observed in addition to the one that originates from the asymmetric A0 mode. The result of the verification experiment is conclusive only if the source of this second resonance is the symmetric S0 mode. Our results show that the second resonance is not generated by the S0 mode. Instead, they indicate that the source is a longitudinal wave propagating in the thickness direction of the paper. We therefore conclude that the applicability of the orthotropic plate wave theory to paper cannot be verified by performing the key experiment that is described in the literature.     

Increased fraction of low-density structures in aqueous solutions of fluoride

X-ray absorption spectroscopy (XAS) and small angle x-ray scattering (SAXS) were utilized to study the effect of fluoride (F(-)) anion in aqueous solutions. XAS spectra show that F(-) increases the number of strong H-bonds, likely between F(-) and water in the first hydration shell. SAXS data show a low-Q scattering intensity increase similar to the effect of a temperature decrease, suggesting an enhanced anomalous scattering behavior in F(-) solutions. Quantitative analysis revealed that fluoride solutions have larger correlation lengths than chloride solutions with the same cations but shorter compared to pure water. This is interpreted as an increased fraction of tetrahedral low-density structures in the solutions due to the presence of the F(-) ions, which act as nucleation centers replacing water in the H-bonding network and forming stronger H-bonds, but the presence of the cations restricts the extension of strong H-bonds.     

Measurement of the flexibility of wet cellulose fibres using atomic force microscopy

Flexibility and modulus of elasticity data for two types of wet cellulose fibres using a direct force–displacement method by means of AFM are reported for never dried wet fibres immersed in water. The flexibilities for the bleached softwood kraft pulp (BSW) fibres are in the range of 4–38 × 10¹² N^?1 m^?2 while the flexibilities for the thermomechanical pulp (TMP) fibres are about one order of magnitude lower. For BSW the modulus of elasticity ranges from 1 to 12 MPa and for TMP between 15–190 MPa. These data are lower than most other available pulp fibre data and comparable to a soft rubber band. Reasons for the difference can be that our measurements with a direct method were performed using never dried fibres immersed in water while other groups have employed indirect methods using pulp with different treatments.     

An improved nicotinic pharmacophore and a stereoselective CoMFA-model for nicotinic agonists acting at the central nicotinic acetylcholine receptors labelled by [3H]-N-methylcarbamylcholine

A study of a series of compounds with agonistic effect at the alpha4beta2 nicotinic acetylcholine receptors resulted in an improved pharmacophore model as well as a CoMFA model. The pharmacophore was composed of three pharmacophoric elements: (1) a site point (a) corresponding to a protonated nitrogen atom, (2) a site point (b) corresponding to an electronegative atom capable of forming a hydrogen bond, and (3) the centre of a heteroaromatic ring or a C=O bond (c). The pharmacophoric elements were related by the following parameters: (a-b) 7.3-8.0 A, (a-c) 6.5-7.4 A, and the angle between the two distance vectors (delta bac) 30.4-35.8 degrees. In addition to this, a stereoselective CoMFA model was developed, which showed good predictability even for compound classes not present in the training set.