Temperature dependence of hydrogen isotope effect in LaNi5-H(D) system

Abstract

To study inverse effect of hydrogen isotopes in LaNi5 for hydrogen isotope separation at ambient temperature, temperature dependence of hydrogen isotope effect in LaNi5－H(D) system was investigated in the temperature range -70 °C to 3 °C. Isotherms of hydrogen isotopes were tested in an automated Sieverts apparatus with a thermostat, and pressure differences were studied between H2 and D2. Isotope exchange process was carried out and H2－HD－D2 equilibrium was judged by online chromatography, separation factors were calculated to investigate the thermodynamic isotope effect. In the H2, D2 isotherms, average time interval (0.5h) between each equilibrium point was relatively short due to high precision temperature control. From the plateau pressures at a constant hydrogen (or deuterium) concentration in LaNi5 (2D or 2H atoms/mole of LaNi5) the partial molar enthalpies, ⊿H, and entropies, ⊿S of formation were calculated. ⊿H and ⊿S kept good accordance with the values from references, which indicated good performance of the Sieverts apparatus. The isotope exchange equilibrium was reached within 1h. The results showed that ratio between H2 pressure and D2 pressure, r(H－D) = P(D2)/P(H2), dropped as temperature decreased and the inverse effect was found (r(H－D)<1.0) below -5 °C according to the absorption branch of isotherms, whereas the effect was estimated to appear below 60 °C from the desorption branch. The separation factor of the H2－HD－D2 mixture, decreased as temperature increased and the inverse effect happened below -20 °C. The inverse effect was affected by the isotherm hysteresis and HD existence.