The use of volatilization reagents is disclosed for improved detection of inorganic oxidizers such as, but not limited to, chlorates and perchlorates. Detection methods are disclosed whereby a reagent can transfer a proton to the anion (i.e., chlorate, perchlorate, etc.) of an inorganic salt analyte, forming an acid (i.e., chloric acid, perchloric acid) that is easier to detect by a mechanism whereby the acidified reagent is more easily vaporized, and hence, more easily detected. Concurrently, the anion of the acid forms a new salt with the cation released from the salt that was acidified. The reagents can also include acidic salts or cation-donators, more generally. In some embodiments, hydrated reagents or co-reagents that can release water can be employed.