Practice of Kinetics (Comprehensive Chemical Kinetics, Volume 1)

3 APPARATUS 61TABLE 9GASEOUS ACTINOMETERSReaction Quantum Wavelength (A) Commentsyield(CH8)&O -+ CO+2CH3. 4co = 1 3200-2500 p > 50 torr; t > 125" C; COdetermined by G SC~(C,H,),CO -+ C0+2CaH6. 4~0 = 0.93 3200-2500 As above. CO only gaseous-+ 1.27product at liquid Ns temp.*CH,CHO +. CH,+CO 4co = 0.30 3130-2380 200 torr; 30" C; alternative to+. CH3+CH0 -+ 1.01 above for temp. below 125".Not very re1iable.c2HI + Is+HI 4~~ = 2.0 3000-1800 0.1 torr to 3.5 atm (of Ns); 4temp.-independent up to 175" C;must be Hg-free system.d2HBr --f Br,+HI 4~~ = 1.0 2500-1800 For conversions of 1 %, 4invariant over a range ofconditions. 100 torr; 25" C.'CO$ -+ co ++O* = 1.0 1600-1200 Fast flow system must beused, otherwise back reactionscomplicate the issue.'30, + 20, 40~ = 2.0 1900-1300 As for CO,.aNaO + Nz+tOs 4~~ = 1.44 1849-1470 Transparent to 2573Aradiation.h2NOC1-+ 2N0 + CI2 $NO = 2.0 6350-3650 Useful for Hg-free systems.'cis-2-butene 2 trans-2-butene q5t-c = 0.5 Hg (SP,)-sensitised reactions.4 independent of pressureabove 30 torr.'D. S. HERR AND W. A. NOYES, JR., J. Am. Chem. SOC., 62 (1940) 2052.K. 0. KUTSCHKE, M. H. J. WIJNEN AND E. W. R. STEACIE, J. Am. Chem. Soc., 74 (1952) 714.F. E. BLACET AND R. K. BRINTON, J. Am. Chem. SOC., 72 (1950) 4715.G. K. ROLLEFSON AND M. BURTON, Photochemistry, Prentice-Hall, New York, 1946, p. 190.G. S. FORBES, J. E. CLINE AND B. C. BRADSHAW, J. Am. Chem. SOC., 60 (1938) 1431.B. H. MAHAN, J. Chem. Phys., 33 (1960) 959.* W. E. VAUGHAN AND W. A. NOYES, JR., J. Am. Chem. Soc., 52 (1930) 559.G. A. CASTELLION AND W. A. NOYES, JR., J. Am. Chem. SOC., 79 (1957) 290.G. B. KISTIAKOWSKY, J. Am. Chem. SOC., 52 (1930) 102.' R. B. CUNDALL, in Progress in Reaction Kinetics, Vol. 2, G. PORTER (Ed.), Pergamon, Oxford,1964, p. 167.References pp. 104-111