This paper deals with a sensitivity analysis of main parameters affecting the measurement of the gas flowrate emitted during testing substances for their potential to emit flammables gases in dangerous quantities where in contact with water, according to the UN N.5 test procedure. UN N.5 is described in the Manual of Tests and Criteria of United Nations (part of the Orange Book) (ONU Manual of Test and Criteria, 2008), serving both applications of international transport regulations as well as classifications of dangerous substances according to Globally the Harmonized System (GHS) and the derived regulation applying in the EU known as 'CLP' Regulation (Regulation (EC) No 1271/2008). The main reason that justifies the present research is that the measurement of emitted gases is highly critical in the final classification resulting from the interpretation of the test results. Moreover, that idea has been raised to adapt the UN N.5 test protocol for classifying, in the future, substances that by contact with water would emit dangerous quantities of toxic gases. Experiments have been carried out to cover the analysis of the influence of ambient temperature, overall volume of glassware, nature of aqueous media, mass sample and sample-to-liquid mass ratio, since such parameters are not fixed within any defined range in the UN N.5 test procedure. The influence of the flow rate measuring device was also considered. Results confirm that the above mentioned parameters may play a significant role to such an extent as to finally alter the final classification resulting from the testing. Guiding principles have also been derived from our measurements and observations towards an improved and more robust UN test protocol in the future.