Traceability of pH measurements by glass electrode cells: performance characteristic of pH electrodes by multi-point calibration

Routine pH measurements are carried out with pH meter-glass electrode assemblies. In most cases the glass and reference electrodes are thereby fashioned into a single probe, the so-called 'combination electrode' or simply 'the pH electrode'. The use of these electrodes is subject to various effects, described below, producing uncertainties of unknown magnitude. Therefore, the measurement of pH of a sample requires a suitable calibration by certified standard buffer solutions (CRMs) traceable to primary pH standards. The procedures in use are based on calibrations at one point, at two points bracketing the sample pH and at a series of points, the so-called multi-point calibration. The multi-point calibration (MPC) is recommended if minimum uncertainty and maximum consistency are required over a wide range of unknown pH values. Details of uncertainty computations for the two-point and MPC procedure are given. Furthermore, the multi-point calibration is a useful tool to characterise the performance of pH electrodes. This is demonstrated with different commercial pH electrodes. ELECTRONIC SUPPLEMENTARY MATERIAL is available if you access this article at http://dx.doi.org/10.1007/s00216-002-1506-5. On that page (frame on the left side), a link takes you directly to the supplementary material.     

Quantum-chemical approach to the elementary steps of plasma etching

We derive for the first time a mechanism of reactive plasma etching in the system Si/F by the quantum-chemical approach. SiF₂-like species at the surface play an important role. SiF₃ surface complexes also occur. The final etching product SiF₄ is formed with high probability in the gas phase.     

Hydrogen–hydrogen bonding in biphenyl revisited

The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface. Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study of the electrostatic potential at the position of the hydrogen nuclei. We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive life.     

Effect of carbonate incorporation on the structural and superconducting properties of the double chain compound Y2Ba4Cu7O15−x

Structural investigations on powder samples of Y₂Ba₄Cu₇O_15–x with different carbonate content have been performed. Powder x-ray Rietveld refinements showed the remarkable influence of carbonate incorporation on the lattice parameters. Most important is the decrease of T_c with increasing carbonate content. We assign these effects to an incorporation of the carbonate ion into the crystal lattice, copper vacancies at the Cu(1) position and a possible misorientation of the copper oxygen single chains. No change of the structure (e. g. superstructure) could be found.     

Derivatives of 2-sulfonamido-4,5-dimethoxyphenylacetic acid and of 2-carboxamido(2-chloroethyl)methylbenzenesulfonamides

Series of variously sustituted amides of 2-sulfonamido-4,5-dimethoxyphenylacetic acid have been prepared. The reaction of diethylamine, piperidine, morpholine and bis(2-chloroethyl)amine with carbo-methoxymethyl-3,4-dimethoxybenzenesulfonyl chloride produced the corresponding sulfonamido derivatives. Acid hydrolysis of the latter and action of thionyl chloride gave the chlorocarboxymethyl-benzenesulfonamides. The acid chlorides of the sulfonamides were transformed to the 2-carboxamido-bis(2-chloroethyl)methylbenzenesulfonamides with bis(2-chloroethyl)amine. These agents were tested in L-1210 and P-388 leukemias and were found not to possess antitumor activity in these two transplantable tumor lines.     

InclusiveK *+(890),K *+(1430) and\bar K^{ * - } (890) production inK + p interactions at 32 GeV/c

We present final results on inclusive production ofK ^*+(890),K ^*+(1430) andK ^*?(890) in \(\bar K^ + p\) interactions at 32 GeV/c, based on a statistics of ～27 events/μb. Total cross sections,p _T -andx-dependence of inclusive distributions are compared with experiments at other energies and with the Lund fragmentation model. Spin density matrix elements of theK ^*+(890) are also discussed. The results suggest that “recombination” of both initial state valence quarks \(\bar s\) andu of theK ⁺ intoK ^*+(890), responsible in the Lund model for ～45% of theK ^*+(890) cross section, is strongly suppressed.     

Neutral strange particle production inK + p interactions at 32 GeV/c

The production properties ofK _s ⁰ , \(\bar \Lambda\) andK ⁺ p interactions at 32 GeV/c are investigated using the final statistics of the experiment. We present total and semi-inclusive cross sections and aver-age multiplicities. Estimates are given of the diffractive dissociation contributions to total and differential cross sections. Thex-,p _T ^?, and transverse mass dependence of inclusive and semi-inclusive distributions is discussed as well as properties of “prompt”K _s ⁰ 's. The ratio of “prompt”K ₈₉₀ ⁺ (K ₈₉₀ ⁰ ) to “prompt”K ⁰ cross sections is measured to be 1.03±0.12 (0.98±0.17). From a comparison of \(\bar \Lambda\) production inK ^± p interactions at 32 GeV/c, we estimate a strange sea-quark suppression of 0.26 ±0.02. The double differential cross sections ofK _s ⁰ 's is studied as a function of Feynman-x andp _T ² , and a Triple-Regge fit performed. The data are compared in detail to versions of the Lund-model for low-p _T hadronic collisions.     

Use of γ-γ Coincidence Spectrometry in the Geochemical Study of Diamictites from South Africa

We used - coincidence spectrometry to investigate the possible presence of a meteoritical component in 27 samples of South African diamictites. Recently, several studies have suggested that some tillites/diamictites may represent impact breccias, but a petrographical study by our group found no evidence for the presence of impact-characteristic shocked minerals. The siderophile elements, such as Cr, Co, Ni, and, especially, the platinum group elements, have high abundances in meteorites, but low abundances in terrestrial crustal rocks. The Ir content of the diamictites was measured with the new iridium coincidence spectrometer (ICS) at the University of Vienna, with detection limits of around 0.02 ppb. No enrichments in the contents of Ir and other siderophile elements compared to average crustal concentrations were found; thus, no unequivocal evidence for an impact origin of these diamictites of the South African Dwyka Group can be documented.     

Spectral studies on VO ions in potassium thiourea bromide single crystals using EPR and optical absorption spectroscopy

Electron paramagnetic resonance (EPR) studies have been carried out on VO²⁺ ions doped in single crystals of ferroelectric material, potassium thiourea bromide (PTB) at room temperature and in the temperature range 103–343 K on X-band MW frequency. An isotropic octet spectrum characteristic of VO²⁺ ion was obtained due to the fast re-orientation of the VO²⁺ in PTB lattice, which exhibits glassy nature at certain range around room temperature. The temperature dependant EPR spectra of VO²⁺ ions in this host lattice has been attributed to the occurrence of multiple phase transitions due to the combined environment effects of KBr and thiourea materials in the single crystal. From the optical absorption spectrum, the crystal field splitting parameter Dq, tetragonal parameters Ds and Dt have been evaluated and discussed.     

Changes in the electrochemical characteristics and u.v.-spectra of polydienyl-lithium chains on storage in polar media

The parallel changes in the electric conductivity and u.v. spectra of polybutadienyl- and polyisoprenyl-lithium (M_nLi) have been investigated in tetrahydrofuran and dimethoxyethane solutions during prolonged storage at 0 and 25°. A considerable dependence of the rate of these changes on the nature of the medium and M_n Li concentration was found. The decrease in the initiating activity during storage has been estimated for the PBLi-THF system.