A new fast response cryogenic evaporative calorimeter.

We present the principle and implementation of a new type of fast response evaporative calorimeter designed to work at cryogenic temperatures and above-ambient pressures. It is capable of measuring input energy from an electric pulse and the thermal output energy by measuring the evaporation of liquid nitrogen through a mass flow meter. This system may be used to measure either the steady heat output from the system submersed under the cryogen or the heat output that results from a fast square-wave profile electrical pulse of duration from 10 µs or longer. The energy output of metal capillary-wire composite systems has been measured calorimetrically. A four-wire measurement was used to monitor the input electric energy with an uncertainty less than 5% for a typical pulse. Mass flow meters and pressure regulation systems were used to monitor the rate of evaporation of liquid nitrogen with a typical precision of 2 std.-ml/min. For a typical pulse, the integrated mass flow of nitrogen could be determined with an uncertainty less than 3%. The pressure controllers and ballast compliance volumes allow the system to return to a steady state of mass flow in less than 2 min following an electric pulse. The system is capable of housing and measuring four separate wire-capillary systems in a single Dewar. On average, a calibration resulted in 3.9 std. ml evaporated per joule of input energy. This corresponds to a 97% efficiency for this calorimeter.

Phase Transition of H2 in Subnanometer Pores Observed at 75 K.

Here we report a phase transition in H2 adsorbed in a locally graphitic Saran carbon with subnanometer pores 0.5-0.65 nm in width, in which two layers of hydrogen can just barely squeeze, provided they pack tightly. The phase transition is observed at 75 K, temperatures far higher than other systems in which an adsorbent is known to increase phase transition temperatures: for instance, H2 melts at 14 K in the bulk, but at 20 K on graphite because the solid H2 is stabilized by the surface structure. Here we observe a transition at 75 K and 77-200 bar: from a low-temperature, low-density phase to a high-temperature, higher density phase. We model the low-density phase as a monolayer commensurate solid composed mostly of para-H2 (the ground nuclear spin state, S = 0) and the high-density phase as an orientationally ordered bilayer commensurate solid composed mostly of ortho-H2 (S = 1). We attribute the increase in density with temperature to the fact that the oblong ortho-H2 can pack more densely. The transition is observed using two experiments. The high-density phase is associated with an increase in neutron backscatter by a factor of 7.0 ± 0.1. Normally, hydrogen produces no backscatter (scattering angle >90°). This backscatter appears along with a discontinuous increase in the excitation mass from 1.2 amu to 21.0 ± 2.3 amu, which we associate with collective nuclear spin excitations in the orientationally ordered phase. Film densities were measured using hydrogen adsorption. No phase transition was observed in H2 adsorbed in control activated carbon materials.