Hydroxylamine (HA), hydroxylamine chloride (HAC1), and hydroxylamine nitrate (HAN) were each mixed with aqueous solutions of Cr3+, Cr6+, Mn7+, Co2+, Co3+, and Cu2+, and their heat flow profiles were monitored by a small-scaled reaction calorimeter, SuperCRC. These mixing tests demonstrated that HA was less reactive than HAC1 and HAN with Mn7+ and Cr6+. Their UV-vis spectra confirmed that the substrates reacted when Mn7+ and Cr6+ were reduced. HA was more reactive with Cu2+ than HAC1 and HAN and exhibited the highest reactivity among the three substrates with regard to metals in the intermediate oxidation states: Cr3+, Co3+ Co2+. During the reaction of HA and Co3+, an induction period was observed. All exothermic reactions were accompanied by precipitation or a change in the UV-vis spectra. (C) 2004 Elsevier B.V. All rights reserved.