OXALITES OF TITANIUM
Abstract
1. Conductometric evidence has been obtained to indicate the presence in solution of four oxalates of titanium, having the molar ratio of oxalic acid to titanium dioxide as 0-5, 1, 1-5 and 2.
2. Only the basic oxalate of titanium, TiOC2O4 3.5 H20, could be isolated in a state of purity. Attempts to isolate the normal oxalate,Ti (C204)2, in a solid form have not been successful.
3. Vapour pressure data on the basic oxalate gave heat of dissociation equal to 15.1K cal. per mole of water, indicating that the water associated with the complex is combined water 4. The basic oxalate yields titanium dioxide, carbon, water, carbon dioxide and carbon monoxide, when heated in vacuum from 80° to 300° C.
5. Structural formula has been assigned to the basic oxalate of titanium.
Rosenheim and Schiitte' claimed to have prepared titanyl oxalate, TiOC2O4 in a syrupy mass, but they could not isolate the substance in solid form. These authors could, however, prepare T10C 204 .C2HSO1-I as crystalline precipitate,soluble in water and (TiO)2 OC2O4. 12 H20 as a solid substance insoluble in water. It has been claimed in many patents 2 that titanyl oxalate, T10C 204 , could be prepared,yet no mention has been made in literature about the preparation and properties of the oxalate. In fact, Sidgwick 3 has recently mentioned that oxalato complexes of titanium like Ti(C2O4)2 and Ti0C204 are not formed. The present investigation was carried out to find whether oxalic acid would combine with titanium hydroxide to give normal oxalate at least in aqueous solution and also to ascertain the nature of the solid obtained from such a solution.
2. Only the basic oxalate of titanium, TiOC2O4 3.5 H20, could be isolated in a state of purity. Attempts to isolate the normal oxalate,Ti (C204)2, in a solid form have not been successful.
3. Vapour pressure data on the basic oxalate gave heat of dissociation equal to 15.1K cal. per mole of water, indicating that the water associated with the complex is combined water 4. The basic oxalate yields titanium dioxide, carbon, water, carbon dioxide and carbon monoxide, when heated in vacuum from 80° to 300° C.
5. Structural formula has been assigned to the basic oxalate of titanium.
Rosenheim and Schiitte' claimed to have prepared titanyl oxalate, TiOC2O4 in a syrupy mass, but they could not isolate the substance in solid form. These authors could, however, prepare T10C 204 .C2HSO1-I as crystalline precipitate,soluble in water and (TiO)2 OC2O4. 12 H20 as a solid substance insoluble in water. It has been claimed in many patents 2 that titanyl oxalate, T10C 204 , could be prepared,yet no mention has been made in literature about the preparation and properties of the oxalate. In fact, Sidgwick 3 has recently mentioned that oxalato complexes of titanium like Ti(C2O4)2 and Ti0C204 are not formed. The present investigation was carried out to find whether oxalic acid would combine with titanium hydroxide to give normal oxalate at least in aqueous solution and also to ascertain the nature of the solid obtained from such a solution.
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