✍ Scribed by Fred B. Wampler
No coin nor oath required. For personal study only.
The photolysis of SO? at 3130 A, FWHM = 165 d, and 22°C has been investigated in the presence of cis-and trans-2-pentene. Quantum yields for the SO, photosensitized isomerization of one isomer to the other have been made for a variation in the [SO,]/[C,HIo] ratio of 3.41-366 for cis-2-C5HI0 and of 1.28-367 for trans-2-C5Hlo. A kinetic analysis of each of these systems permitted new estimates to be made for the SO, collisionally induced intersystem crossing ratio a t 3130 A from SO2(lB1) to S 0 2 ( 3 B I ) . The estimates of kla/(kIa + k l b ) obtained are 0.12 f 0.01 arid 0.12 =k 0.02 (two different kinetic analyses in the cis-2-C5Hlo study) and 0.20 f 0.05 and 0.20 f 0.04 (two different kinetic analyses in the trans-2-C5Hlo study).
Collisionally induced intersystem crossing ratios of kza/(kza + kzb) = 0.51 & 0.10 and k3J (ksa + k3b) = 0.62 f 0.12 were obtained for cis-and trans-2-pentene, respectively. Quenching rate constants a t 22°C for removal of S02(3Bi) molecules by cis-and trans-2-CSHlo were estimated as (1.00 f 0.29) X 1Ol1 I./mole.sec and (0.857 f 0.160) X 10" I./mole.sec, respectively. Prolonged irradiations, extrapolated to infinite irradiation times, for mixtures initially containing SO, and pure isomer, either the cis or trans, yielded a photostationary composition of [trans-2-pentene]/[cis-2-pentene] = 2.1 f 0.1.
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