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The concentrations of S2O32- and SO32- were measured in gold leaching systems, including thiosulfate system, polysulfide system and the modified lime sulfur synthetic solution (ML) system in the process of chemical reaction. The interactions among S2O32-, SO32- and S2- were discussed. The behavior mechanism of sulfur-bearing reagents was proposed to describe the process reactions and their Gibbs free energy. The proper quantity oxygen and SO32- reduce decomposition of S2O32- and react with sulfur derived from the decomposition of SX2-. So, SO32- ions have action to stabilize sulfur-bearing system and are favorable to leach gold.