Volatilization reagents are disclosed for improved detection of inorganic oxidizers such as chlorates and perchlorates by mass spectrometry. Thermal desorption methods are also disclosed in which the reagent transfers 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 more easily vaporized and, hence, more easily detected. The reagents can include acidic salts or cation-donators, more generally. The class of reagents including polymeric acids, polymeric organic acids and polymeric sulfonic acids. Hydrated reagents or other reagents that can release water can also be employed as co-reagents. Further, these reagents can be embedded in a swipe or other substrate, delivered as a liquid infused via nebulizer, or otherwise introduced to a sample to be tested.