Extraction of Ferric Chloride by Isopropyl Ether 2573 Himmelstem82 has found an increase of pressure from 1 to 968 atm. to increase the atomic ratio found on electrolysis by a negligible amount (from 0.7 to not more than 0.707).
SummarySeven isotherms, from 200 to 313°, have been traced on the pressure-composition diagram for palladium and hydrogen, in most cases from zero pressure through the heterogeneous region and well into the second homogeneous solid phase. The diagram, including the previous results at lower temperatures of Gillespie and Hall, indicates that the compounds PdsH, Pd3H, PcfiH and Pd8H have chemical individuality, even though in the second case, and possibly others, the tangent to the boundary curve is not vertical, the curve then resembling the analogous curve for FeO in the Fe-H-0 system. In all cases the (22) Von Samson-Himmelstern, Z. anorg. Chem., 186, 337 (1930).compound is to be regarded as a solid solution that has a stoichiometrical composition over a limited range of temperature. The finding of Briining and Sieverts of a critical solution temperature for the solid phases near 300°is confirmed, and the critical constants are found to be: temperature, 295,3°; pressure, 19.87 atm. and atomic ratio H:Pd, 0.270.In the discussion the validity is denied of (1) certain evidence against the existence of PdsH, and (2) certain evidence in favor of the existence of PdH.Mention is made of palladium mercuride, probably PdiHgs, of very low decomposition pressure. The palladium investigated was found at the conclusion of the experiments to contain a presumably harmless amount of mercury, much less than 0.2%. Cambridge, Mass.
Rate measurementshave shown that the hydrolysis of thioacetamide to acetamide and hydrogen sulfide in dilute acid solutions is first order with respect to both thioacetamide and hydrogen ion concentrations; only a small fraction of the acetamide formed was hydrolyzed to acetic acid and ammonia.The second-order rate constant for the hydrolysis reaction was found to be 0.21 ± 0.023 liter per mole per minute at 90°C. and the energy of activation was calculated to be 19.1 kcal per mole through the temperature range from 60°to 90°C. The assumption that thioacetamide hydrolyzes rapidly and quantitatively in hot acid solutions and can be substituted for hydrogen sulfide without modification of procedure is not valid. In solutions having pH values less than 3 the precipitation of lead sulfide by thioacetamide proceeds through hydrolysis of the latter; the rate of precipitation quantitatively follows the rate of hydrolysis. In solutions having pH values from 5.1 to 3.5 the precipitation is first order with respect to both thioacetamide and lead ion concentrations and inversely half order with respect to hydrogen ion concentration.The velocity constant for the expression -d[Pb(II)]/dt = fc[Pb(II)][CH3CSNH2]/[m12 was found to be 1.13 X 10-3 liter 1,2 mole-112 minute-1 at 90°C. in 0.081.M sodium formate, and the energy of activation was calculated to be 15.5 kcal per mole. At pH 5 the rate of precipitation of lead sulfide can be a thousand times greater than the rate of formation of hydrogen sulfide by hydrolysis of the thioacetamide.
Electrolytically generated bromine can be used for the titration of micro gram quantities of thiodiglycol. The presence of excess bromine can be detected and
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