Hydrogen Peroxide and Its Analogues: V. Phase Equilibria in the System D2o–d2o2

The cooling curves of a number of solutions of deuterium peroxide in heavy water in the concentration range 11% to 95% were measured in order to determine the solid-liquid phase diagram for that binary system. The apparatus of Herington and Handley, which uses a pulsing pressure for stirring the solutions, and a thermistor, was found to be particularly suitable for that purpose. As could be expected the freezing-point curve of the deuterated compounds is closely similar to that of the hydrogen compounds, being shifted up only by about 4° for water-rich solutions and by 2° for peroxide-rich solutions. The melting point of the addition compound, D2O.2D2O very nearly coincides with one of the eutectic points at 46.2% D2O2 and −51.5 °C.; the other eutectic point is at 60.5% D2O2 and −55.1 °C. By extrapolation the melting point of pure deuterium peroxide is found to be 1.5 °C. as compared with −0.43 °C. for hydrogen peroxide. Concentrated solutions of deuterium peroxide exhibit an extreme tendency to supercool, resulting sometimes in formation of glasses even at liquid-air temperature. The previous results of Foley and Giguère for the system H2O–H2O2 were confirmed, specially as regards the melting point of the addition compound H2O2•2H2O.