15. The following mechanism has been pro- posed to explain the kinetics of the radiation curing process for elastomeric polyurethanes and polythio ethers. Initiation: RSH + hy “5 RS + He reaction rate = k,1 (RSH) where I is the in- tensity of the incident radiation Chain transfer He + RSH SH, + RS: Propagation: RS: +C! RSCH,—CHR CHR’ RSCH,—CHR® RSH “5 RS- + RSCH,CH,R’ ‘Termination: ans: 4S RSSR (a) In terms of the usual Bodenstein steady- state approximation, derive an expression for the net rate of disappearance of thiol (RSH) in terms of the concentrations of stable species and the various rate constants. Reactions 3 and 4 occur at rates that are much greater than those for the other reactions. (b) The following data have been reported for the Co" irradiation of an equimola: solu- tion of RSH and CH,=CHR’ using a con- stant dose rate. ‘Thiol concentration Time, t (sec) (kmolesim?) 0 oT 300 0510 600 0478 900 0.432 1280 0382 1800 0343 3710 0.223 Note that the overall stoichiometry of the propagation steps is: RSH + CH,=CHR’ + RSCH,—CH,R’ Is this data consistent with the mechanism. proposed in part (a)?1. The oxidation of iodide ions by hydrogen peroxide H,0, + 2H* 4 217 + 2H,0 + 1, has been studied by Bell et al. [J. Phys. Chem, 55 (874), 1951]. At 25 °C the reaction appears to proceed by two parallel paths so that the ob- served rate expression is of the form r = k,(H20,)(I7) + k2(H202)0-)(H*) The influence of ionic strength on the two rate constants was noted to be as follows. ky ky u(kmoles/m?) (m3/kmoles'sec)_ (m*/kmoles* 0.000 0.658 19.0 0.0207 0.663 15.0 0.0525 0.670 12.2 0.0925 0.679 113 0.1575 0.694 9.7 0.2025 0.705 92 Are these data consistent with the results predicted by equation 7.1.4?13, Garratt and Thompson [J. Chem. Soc., 1934, 524, 1817, 1822] have studied the photochemi- cal and thermal decomposition of nickel tetra- carbonyl. Later work by Day, Pearson and Basolo [J. Am. Chem. Soc., 90 (6933), 1968] confirmed that the rate law postulated by Garratt and Thompson was obeyed for the homogeneous process. The mechanism postu- lated by both groups is: k Ni(CO), = Ni(CO); + CO in Ni(CO), 3 Ni + 3CO (a) What rate law is consistent with this mechanism? (b) Callear [Proc. Roy. Soc. A265 (71), 1961] has also investigated the decomposition of Ni(CO),, but he used a flash photolysis approach. He proposed the following mech- anism. Ni(CO), = Ni(CO); + CO Ni(CO); = Ni(CO), + CO Ni(CO), “S Ni(s) + 2CO Under what conditions are the two mecha- nisms equivalent?