Polarographic Behaviour of the Hexa-ammine-chromium(III) Ion: Role of Hydrogen Ions
HEXA-AMMINECHROMIUM(III) ion in acetate buffer solutions is reduced at the dropping mercury electrode, and gives two polarographic waves. The first wave, which is well defined, is considered to be a one-electron reduction of Cr(III) to Cr(II)1. Its half-wave potential at 25° C was found to be −0.970 V versus saturated calomel electrode in 0.1 M acetate buffer solution which contained 0.9 M potassium chloride and 0.005 per cent gelatin (Fig. 1, curve a). The limiting current of this wave was diffusion-controlled and proportional to the concentration of the complex ion up to 5 mM. Both the half-wave potential and the diffusion current remained constant when the pH was varied from 4.5 to 5.45. No change was observed when potassium chloride was replaced by ammonium chloride at the constant ionic strength. The plot of log ī/(īd − ī) versus E, where ī means the average current, īd the average diffusion current, and E, the potential of the dropping mercury electrode, gave a straight line with a reciprocal slope of 64 mV, whereas the examinations with Kalousek's circuit and alternating current polarograph showed that this wave has nearly irreversible character.
Ion-pair Formation of Some Substitution-inert Complexes and Sulfate Ions. Determination of Association Constants Using Polarographic Diffusion Current
The polarographic diffusion current of some tervalent substitution-inert complex cations decreases by the addition of sulfate. From the change in diffusion current the association constants of substitution-inert complex and sulfate ions are obtained at ionic strength 0.1 (NaClO4) and 25°C. The values are 69±8, 58±8 and 4×10 for [Co(NH3)6]3+–SO42−, [Cr(NH3)6]3+–SO42− and [Cr(H2O)6]3+–SO42 respectively. The formation of [Co(NH3)6]3+–HSO4− is negligibly small compared with that of [Co(NH3)6]3+–SO42−.
Far-field dispersal modeling for fuel-air-explosive devices
A computer model for simulating the explosive dispersal of a fuel agent in the far-field regime is described and is applied to a wide variety of initial conditions to judge their effect upon the resulting fuel/air cloud. This work was directed toward modeling the dispersal process associated with Fuel-Air-Explosives devices. The far-field dispersal regime is taken to be that time after the initial burster charge detonation in which the shock forces no longer dominate the flow field and initial canister and fuel mass breakup has occurred. The model was applied to a low vapor pressure fuel, a high vapor pressure fuel and a solid fuel. A strong dependence of the final cloud characteristics upon the initial droplet size distribution was demonstrated. The predicted fuel-air clouds were highly non-uniform in concentration. 18 refs., 86 figs., 4 tabs.