Solubility Product of Metal Dithiophosphates

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-