Protocols for traceability in chemical analysis

 The authors propose definitions and terminology for protocols on traceability links, generally to the international system of units, for specific chemical-analytical measurements in accordance with recognized principles of science. These definitions and terms could be useful in science, technology, commerce or law. A chain of such links leads from a measurand in a sample up to a unit in the International System of Units or, if unavailable, to a value on an internationally recognized measurement scale. The quality of such a chain is quantified by combining all recognized uncertainties estimated for all its links. These uncertainties of the measured values arise from many potential error sources. The protocols should give details of specific uses of reference materials, measuring instruments and standard measurement methods. Received: 12 January 1997 Accepted: 31 January 1997     

Threshold tolerance graphs

In this paper, we introduce a class of graphs that generalize threshold graphs by introducing threshold tolerances. Several characterizations of these graphs are presented, one of which leads to a polynomial-time recognition algorithm. It is also shown that the complements of these graphs contain interval graphs and threshold graphs, and are contained in the subclass of chordal graphs called strongly chordal graphs, and in the class of interval tolerance graphs.     

Measurement principles for traceability in chemical analysis

 By the definition of the mole as a base unit for amount-of-substance measures within the International System of Units (SI), chemists can make chemical measurements in full compliance with established metrological principles. Since the mole requires exact knowledge of the chemical entity, which is often neither available nor of practical relevance to the purpose of the measurement, the SI units of mass or length (for volume) are unavoidable in the expression of results of many chemical measurements. Science, technology, and trade depend upon a huge and ever increasing number and variety of chemical determinations to quantify material composition and quality. Thus, international harmonization in the assessments of processes, procedures, and results is highly desirable and clearly cost effective. The authors, with relevant experience and responsibilities in Europe and America, have found some consensus in the interpretation of the metrological principles for chemical measurements, but believe open discussion should precede wide implementation by chemical communities. In fostering this dialogue, this paper shows, for instance, that more precise interpretation of the definitions for "traceability," "calibration," and "validation" is needed for present-day chemical measurements. Problems that face scientists in making measurements do not all vanish just by adherence to the SI. However, such compliance can improve communication among chemists and metrologists. Received: 30 June 1995 Accepted: 30 June 1995     

An improved one-step method to prepare some diaza-crown ethers and the cation complexation properties of 4,10-diaza-18-crown-6 with two transition metal ions

4,10-Diaza-15-crown-5, 4,10-diaza-18-crown-6, 4,13-diaza-21-crown-7, and 4,16-diaza-24-crown-8 were prepared by an improved method from the appropriate oligothylene glycol diiodides and diamines. The thermodynamic values of log K, ΔH and ΔS for the interaction of 4,10-diaza-18-crown-6 with Pb²⁺ and Ag⁺ were determined by a calorimetric titration method and compared with thermodynamic values for interactions of 4,13-diaza-18-crown-6 with the same cations. The thermodynamic values were found to be different for the two diaza-crown ligands. 4,10-Diaza-18-crown-6 and its 4,13-diaza-crown analog formed precipitates when treated with Co²⁺, Cd²⁺, Cu²⁺, and Ni²⁺ so that no thermodynamic data are reported for these interactions.