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Explosion and decomposition limits of flammable and chemically unstable gases were determined experimentally in a closed autoclave with an ignition energy higher than the standard 10 J a 20 J. The ignition source was a lightning arc caused by an exploding wire igniter as described in EN 1839 B. With a newly developed ignition system a graded ignition energy between 3 J and 1000 J was generated. Different types of gases were studied with this ignition system: methane as a typical fuel gas and reference gas for some standards for explosion limit determination, the refrigerant R32 (difluoromethane) as a mildly flammable gas with low burning velocity and high minimum ignition energy compared with methane as well as the chemical unstable gases acetylene, nitrous oxide and ethylene oxide, which can decompose explosively in the absence of air or other oxidizers. It was found that the influence of strong ignition sources on explosion and decomposition limits can be very different for different systems. In case of methane only the upper explosion limit was influenced significantly by the ignition energy, whereas the lower explosion limit was constant. In a standard test vessel with an inner volume of 14 dm3 it was difficult to quantify the upper explosion limit of methane exactly with the strong ignition source, because the explosion pressure did not increase abruptly near the explosion limit, but steadily over a large concentration range. Probably a larger explosion vessel is more appropriate in this case. In case of R32 however, it was the lower explosion limit that was influenced significantly by the ignition energy and not the upper explosion limit. A particularly strong dependency from the ignition energy was found for the decomposition limits of the chemically unstable gases in nitrogen. Here special regard is necessary in practical applications, if uncommonly strong ignition sources cannot be excluded.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given here of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and its new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This article summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under non-atmospheric conditions are given.
Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances
(2019)
Due to the fast development and availability of computers, predictive approaches are increasingly used in the evaluation process of hazardous substances complementary to experiments. Their use was recommended as alternative to experimental testing by the REACH regulation to complete the lack of knowledge on properties for existing substances that must be registered before 2018 (upon quantities). Among the proposed predictive approaches, Quantitative Structure Property Relationships (QSPR) are powerful methods to predict macroscopic properties from the only molecular structure of substances. In that context, the HAZPRED project (2015-2018, founded by the SAF€RA consortium) aims to develop theoretical models (e.g. QSPR) and small-scale tests to predict complex physico-chemical properties (e.g. thermal stability, explosivity) of hazardous substances to complete the lack of knowledge on these hazardous substances quickly or to understand their decomposition behaviour better. In particular, this contribution will present the work done in this project on the physical hazards of organic peroxides and self-reactive substances: gathering of existing experimental data, new experimental campaigns, review of existing models and proposition of new estimation methods.
The explosion regions of 1-propanol, 2-propanol, acetone and 1-butanol in air were measured in the presence of CO2, He, N2 and Ar in accordance with EN1839 method T at high temperatures and at atmospheric pressure. The experimental results show that 1-propanol, 2-propanol and acetone have very similar lower explosion limits (LELs). 1-Butanol shows a slightly wider explosion area near the LEL line. In addition, the explosion regions of all combustible/inert gas/air mixtures were calculated with the method of constant adiabatic flame temperature profiles (CAFTP), using the flame temperature profile along the explosion region boundary curve of each combustible/N2/air mixture as a reference to determine the explosion regions of combustible/inert gas/air mixtures with inert gases other than N2 at different initial temperatures. To calculate the explosion regions for systems containing He, the calculation method was modified to include the very different physical transport properties of He. Moreover, the procedure for calculating the apexes in the ternary explosion diagrams was modified. The calculation results show good agreement with the experimental results.
CEQAT-DGHS Interlaboratory Test Programme for Chemical Safety - Need of Test Methods Validation
(2019)
Safety experts, manufacturers, suppliers, importers, employers or consumers must be able to rely on the validity of safety-related test methods and on correct test results and assessments in the laboratory. Via the eChemPortal lots of data from the REACH registration dossiers are available. However, the quality and correctness of the information remains in the responsibility of the data submitter. Unfortunately, we found more or less appropriate information on physicochemical properties and concluded that more quality or adequacy of any data submitted will be needed.
Interlaboratory tests play a decisive role in assessing the reliability of test results. Interlaboratory tests on different test methods have been performed by Bundesanstalt für Materialforschung und –prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB) in collaboration with the QuoData GmbH during the last 10 years. Significant differences between the results of the participating laboratories were observed in all interlaboratory tests. The deviations of the test results were not caused only by laboratory faults but also by deficiencies of the test method.
In view of the interlaboratory test results the following conclusions can be drawn:
• To avoid any discrepancy on classification and labelling of chemicals it should become state of the art to use validated test methods and the results accompanied by the measurement uncertainty.
• A need for improvement is demonstrated for all examined test methods. Thus, interlaboratory tests shall initially aim at the development, improvement and validation of the test methods and not on proficiency tests.
• The laboratory management and the practical execution of the tests need to be improved in many laboratories.
• The term "experience of the examiner" must be seen critically: A "long experience with many tests" is not necessarily a guarantee for correct results.