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In order to decrease the evaporating rate of ammonia and increase the solubility of copper in the solution, ethylenediamine was added into the ammonia-ammonium chloride system to leach the copper containing oxide ores.The solubility of malachite Cu2(OH)2CO3 in ammonia-ammonium chloride-ethylenediamine(En)-water system was calculated using the exponential computation method based on both mass balance and charge balance equations.The conditions of malachite Cu2(OH)2CO3 converting to atacamite Cu(OH)1.5Cl0.5 were studied.A group of experiments were designed to validate the veracity of the results of the thermodynamic calculation.