About 50 percent of the I128 atoms formed by the I127(n, γ)I128 reaction in gaseous mixtures of 0.2 mm of iodine and 400 mm of methane enter combination as methyl iodide, whereas much less than 1 percent of iodine atoms produced simultaneously by the photochemical dissociation of the iodine do so. By contrast, about 1 percent of the I128 formed by the I127(n, γ)I128 reaction in gaseous mixtures of iodine and ethyl iodide enters organic combination.
The solubility of iodine in pure liquid methane is less than 10−10 m/1 but as much as 3×10−5 m/1 may be dissolved when air has been allowed to condense in the methane. In such solutions I128 from the I127(n, γ)I128 reaction is able to enter organic combination as methyl iodide, ethyl iodide, and higher boiling material.
The hydrolysis kinetics of ClCN have been reinvestigated from pH 0.0-10.5 and from 18-40°C. In the pH range from 1-5, the hydrolysis rate is invariant and the activation parameters (4H' = 84 k J mol-' and 4s' = -84 J mol-' K-') are consistent with water attack. In basic solution the rate is first order each in ClCN and OH-concentrations with parameters 4H' and A S r equal to 82 kJ mol-' and +54 J mol-' K-', respectively.The rate constants with 20 other donors have been measured. Nitrogen nucleophiles are more reactive than oxygen donors, and an alpha-effect is seen. The constants follow a pattern indicative of attack at carbon. Cyanate in its acid form reacts with nucleophiles. Further points on the cyanate rate-pH profile have been obtained. A chromate-catalyzed hydrolysis can contribute between pH 5-10. Some studies were made of the reaction of cyanate with hydrogen peroxide. Free energy correlations are presented.
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