Measurement uncertainty and the use of reference materials

The use of (certified) reference materials and quality control materials can form a suitable basis for evaluating measurement uncertainty of routine measurements. In particular when these materials are used for quality control purposes, it is not always evident how the quality control data can be used in the uncertainty budget of a routine measurement. Current guidance documents on the evaluation of measurement uncertainty and the use of reference materials treat this subject only in part, or in very generic terms. ISO/REMCO has established a new working group that will provide practical guidance and examples on how to use quality control data in the evaluation of measurement uncertainty. A short introduction to the subject is given.

Update on COMAR: the Internet database for certified reference materials

This paper describes the COMAR database for certified reference materials (CRMs). The Web-based version of COMAR is freely accessible via the Internet. COMAR was established to assist laboratories in finding the CRMs needed. The database is maintained in a collaboration of the world’s major CRM producers. The planned changes in the database as agreed at the last COMAR council meeting in Prague in May 2006 are indicated.

The meaning of ‘concentration’

Terminology within a small laboratory community can be informal without danger of misunderstanding, but communication with a wider audience and not least in publications, needs unequivocal terms for defined concepts. As an example, the many meanings of “concentration” are explored to present a systematic nomenclature, including a concept diagram.

Food anaphylaxis

    Figure Avoidance is the primary measure in food allergy confirmed

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ISO 5725 and GUM: comparison and comments

We compare the approach to measure uncertainties proposed in ISO 5725 and GUM from a statistician point of view. In particular we give some warnings to the application of the expanded uncertainty introduced in GUM when the input variables are few and we report some considerations on the relevant role of the interactions among the input variables in the measurement equation as well as the role of statistical design of experiments to measure uncertainties.

Kinetics of substitution at [tris(3,5-dimethylpyrazolyl)-hydroborato]molybdenum nitrosyl dihalides by alcohols and by aniline

The kinetics of substitution by alcohols and by aniline at [tris(3,5-dimethylpyrazolyl)hydroborato]molybdenum nitrosyl dihalides in toluene solution at 298.2 K and at atmospheric pressure are reported and interpreted in terms of an associative mechanism.

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Replicated observations in metrology and testing: modelling repeated and non-repeated measurements

In order to choose the right statistical tool, a basic issue for an accurate analysis of each specific problem is to understand whether the set of replicated measurement results under examination is to be considered as pertaining to repeated measurements or not. This issue is particularly important, since most of the traditional tools are valid only for repeated measurements, but, in many cases, such as laboratory comparisons (in metrology and in testing), the measurements necessary to assess correctly the measurand value and the associated uncertainty do not represent repeated measurements. The analysis performed in this paper aims to shine some light on these issues, starting with a review of the basic concepts, such as repeatability, reproducibility, accuracy, systematic error and bias, as defined in international documents and as used in the literature. The paper shows that, currently, a full consensus on a common language and understanding has not yet been achieved, and then shows how this fact reflects on the basic data models, especially those concerning inter-comparison data.

Core-shell effects of functionalized oxide nanoparticles inside long-range meso-ordered spray-dried silica spheres

Core-shell and homogeneous distributions of functionalized cerium oxide nanoparticles within spray-dried mesostructured silica spheres are achieved by modification of synthesis parameters such as the templating agent and nanoparticle capping functions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

In defence of the correlation coefficient

The relationship between calibrated range, residual standard deviation and correlation coefficient r is discussed. It is shown that in typical chemical calibration applications with appropriately distributed calibration points (particularly, with range comparable to mean and with approximately even or with ‘successive dilution’ spacing), the linear correlation coefficient has valid application as a routine criterion for acceptable fit if used with due care.

Metrological traceability: I make it 42; you make it 42; but is it the same 42?

The paper reproduces a talk given at a 2-day symposium on quality assurance in chemistry held in Brisbane, Australia in 2005. Intended for an audience of analysts in the field, the theme of the symposium drew inspiration from the series of books by Douglas Adams “The Hitchhiker's Guide to the Galaxy”. An introduction to basic concepts of metrological traceability is followed by a discussion of practical steps to ensure metrological traceability of field measurement results. The relationship between metrological traceability and comparability of measurement results is discussed. To achieve metrological traceability in the field, the use of appropriate certified reference materials for calibration is recommended. Examples of atmospheric carbon dioxide and roadside breathalyzer measurements are given.

Development of candidate reference materials for the measurement of lead in bone

The production of modest quantities of candidate bone lead (Pb) reference materials is described, and an optimized production procedure is presented. The reference materials were developed to enable an assessment of the interlaboratory agreement of laboratories measuring Pb in bone; method validation; and for calibration of solid sampling techniques such as laser ablation ICP-MS. Long bones obtained from Pb-dosed and undosed animals were selected to produce four different pools of a candidate powdered bone reference material. The Pb concentrations of these pools reflect both environmental and occupational exposure levels in humans. The animal bones were harvested post mortem, cleaned, defatted, and broken into pieces using the brittle fracture technique at liquid nitrogen temperature. The bone pieces were then ground in a knife mill to produce fragments of 2-mm size. These were further ground in an ultra-centrifugal mill, resulting in finely powdered bone material that was homogenized and then sampled-scooped into vials. Testing for contamination and homogeneity was performed via instrumental methods of analysis.

Core-shell structured electrode materials for lithium ion batteries

Recent progress in studies of several types of core-shell structured electrode materials, including TiO₂/C, Si/C, Si/SiO _x , LiCoO₂/C, and LiFePO₄/C nanocomposites, including details of their preparation and their electrochemical performance is briefly reviewed. Results clearly show that the coating shell can effectively prevent the aggregation of the nanosized cores, which are the electrochemically active materials. In addition, the diffusion coefficients of lithium ions can be increased, and the reversibility of lithium intercalation and deintercalation is improved. As a result, the cycling behavior is greatly improved. The reviewed results suggest that core-shell nanocomposites are a good starting point for further development of new promising electrode materials.

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Stress generation and fracture in lithium insertion materials

A mathematical model that calculates volume expansion and contraction and concentration and stress profiles during lithium insertion into and extraction from a spherical particle of electrode material has been developed. The maximum stress in the particle has been determined as a function of dimensionless current, which includes the charge rate, particle size, and diffusion coefficient. The effects of pressure-driven diffusion and nonideal interactions between the lithium and host material have also been described. The model predicts that carbonaceous particles will fracture in high-power applications such as hybrid-electric vehicle batteries.

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Do we need to rethink collaborative trials?

The currently recommended design of collaborative trials (interlaboratory method performance studies) is examined in relation to the usefulness of the resulting statistics. It is suggested that larger experiments, without duplicate analysis, would be more informative.

Strategic views of accreditation

This paper summarises the experience we gained while going through an accreditation process in accordance with the requirements of ISO/IEC 17025 Standard. We propose in this paper an initial path finding study stage to evaluate the laboratory's predisposition for, and the benefits of, accreditation. We also present a conceptual framework as part of the path finding study stage to identify and classify different groups of activities in a laboratory into separate business domains. The objective of the study is to assess, for each business domain, the approach, the benefits, costs and implications of working with a systematic QA and then design a priori appropriate working systems tailored to the real needs of each business. Such a study should naturally lead to an appropriate definition of accreditation scope.

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A note on Michael Weisberg’s: challenges to the structural conception of chemical bonding

Michael Weisberg’s recent 2007 paper on the chemical bond makes the claim that the chemical notion of the covalent bond is in trouble. This note casts doubts on that claim.

Chemistry, commentary, and community: discussion of “an examination of the vaporization enthalpies and vapor pressures of pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine” by Lipkind and Chickos

Vaporization enthalpies for the isomeric diazines were discussed within the context of recent measurements and estimation techniques. It is suggested that pyridazine shows enigmatic behavior.

NMR and HPLC study of chiral selectors with naphthyl unit

Doubling of resonances in NMR spectra of chiral selectors with naphthyl group attached to the tertiary amide nitrogen atom has been noticed what revealed the presence of two isomers. To test the enantiorecognition ability of these chiral selectors they are covalently bonded to the HPLC silica gel. Those kind of chiral stationary phases were compared with analogous commercial leucine chiral stationary phase. They exhibit the better enantioseparation results which indicate that the existence of cis/trans isomers does not have the negative influence on their enantioselective ability.

A novel Ce<Superscript>III</Superscript>-cyclam type complex and its redox chemistry in aqueous solutions

A new Ce^III complex was synthesized by mixing the ligand “dioxocyclam” with Ce^III ions at pH 8.0 and its redox properties were investigated.

NEMCA effect: why are the work function changes of the gas exposed catalyst-electrode surface one-to-one related to the changes in the catalyst working electrode potential?

In the present work, an important point concerning the NEMCA effect is addressed. We analyse the reasons why the changes in the work function of the gas exposed catalyst-electrode surface are one to one related to the changes in the catalyst working electrode potential E with respect to a reference electrode. It is concluded that this is due to the unique properties of the catalyst/solid electrolyte interface: the structure of the double layer in this region is very different from that in liquid electrolytes, being the potential difference at this interface mainly determined by the specific adsorption of the mobile species in the solid electrolyte.