Methods of enhancing the segregation roast through the use of microwave radiation and chloride ions are disclosed. The processes provide means of recovering metals trapped in ores and slags by reaction of these materials with carbon, chloride and water using microwave radiation as the primary energy source. The metals may be present in starting materials such as metallic sulfides, slags, metallic oxides such as laterites, magnetites, iron oxides, silicates and carbonates. The metals are reduced and can be recovered by separation from the gangue. Water, carbon and chloride can be recycled to the reaction to reduce costs.