The global copper industry faces a technological challenge to develop processing schemes for more complex and impure ores and concentrates. Group 15 elements (As, Sb, and Bi) represent impurities that are troublesome both in terms of environmental impact and metallurgical processing. The so-call "dirty" copper concentrates are either unacceptable for smelting and refining or incur high penalties. The behavior of the Group 15 elements is of critical importance in maintaining product quality and process performance. During copper electrorefining, these impurities are released to the electrolyte by electrochemical dissolution of the anode. Depending mainly on temperature, concentration, and oxidation state these elements can spontaneously coprecipitate from the electrolyte. Some of these precipitates are referred to as floating slimes and their formation can have extremely detrimental effects on cathode purity. In this paper, the mechanism of floating slimes formation will be discussed and the fundamental thermochemistry will be reviewed and analyzed in relation to solubility properties.