Novel concept for the mass spectrometric determination of absolute isotopic abundances with improved measurement uncertainty: Part 2 – Development of an experimental procedure for the determination of the molar mass of silicon using MC-ICP-MS

The isotopic abundances and thus molar mass M(Si) of a silicon crystal material with natural isotopic abundances have been measured for the first time using multicollector-ICP-mass spectrometry (MC-ICP-MS) in combination with a novel concept of a modified isotope dilution mass spectrometry (IDMS)-method. This experimental work is the further development of part 1 of this series of papers. While part 1 describes the theoretical background and the mathematical derivation of the novel concept in detail, the measurements presented here serve to validate the novel concept and give experimental proof of its capability. Moreover, the also new method for the analytical calculation of calibration factors needed in the determination of absolute isotope amount ratios has been tested successfully. Silicon isotopic abundances have been measured directly from an aqueous alkaline matrix following a new sample preparation protocol developed within the framework of this study. A molar mass of M(Si) = 28.08548(13) g/mol with an associated relative uncertainty of urel = 4.6 × 10−6 (k = 1) has been measured. This is in excellent agreement with the current IUPAC value for the molar mass of natural silicon M(Sinat) = 28.08550(15) g/mol with urel = 5.3 × 10−6 (k = 1). An uncertainty budget according to the Guide to the Expression of Uncertainty in Measurement (GUM) was calculated to assess the presented results and to validate the novel concept with the help of experimental data. The development of a new experimental procedure is presented in detail and the contributions to the uncertainty are discussed in comparison to part 1 of this work.

The applicability of the theoretical procedure (part 1) was successfully proven by the experimental determination of the molar mass of natural silicon.Figure optionsDownload high-quality image (72 K)Download as PowerPoint slideResearch highlights▶ Measurement of the molar mass of natural silicon (Avogadro-project). ▶ Description of the combined MC-ICP-MS- and modified IDMS-experiment. ▶ Analytical measurement of isotope amount ratio calibration factors. ▶ Uncertainty budget of molar mass of silicon according to GUM.