Formic acid in hydrogen: is it stable in a gas container?

Formic acid is an intermediate of the steam methane reforming process for hydrogen production. According to International Standard ISO 14687, the amount fraction level of formic acid present in the hydrogen supplied to fuel cell electric vehicles must not exceed 200 nmol·mol−1. The development of formic acid standards in hydrogen is crucial to validate the analytical results and ensure measurement reliability for the fuel cell electric vehicles industry. NPL demonstrated that these standards can be gravimetrically prepared and validated at 4 to 100 µmol·mol−1, with a shelf-life of 1 year (stability uncertainty < 7%; k = 2). Stability was not affected over 1 year or by low temperature or pressure. At sub-µmol·mol−1 level, formic acid amount fraction was found to decrease due to adsorption on the gas cylinder surface; however, it is possible to certify the formic acid amount fraction after a period of 20 days and ensure the certified value validity for 1 year with an uncertainty below 7% (k = 1) confirmed by thermodynamic investigation. This study demonstrated that formic acid in hydrogen gas reference materials can be prepared with reasonable uncertainty (>7%, k = 1) and shelf life (>1 year). Potential applications include the calibration of analysers and for studying the impact of formic acid on future application with relevant traceability and accuracy.