HEiXRY LINSCHITZ 



177 



TABLE 1 (3) 



Kinetics of Chemiluminescent Zn-Porpuvrin-Catalvzed 

 Decomposition of Tetralin Hydroperoxide 



Run: PZL-60 Temp: 148.0° C. 



S = Photometer Sensitivity Correction (^^0.98) 



ki (corr.) = ( ' 



kz = 



kr = 



d/ A,a. [THPj [ZnTPPI 

 d[ZnTPP] 1 1 



d/ 

 1 



[THP]'^ [ZnTPPJ 

 1 



S [THP] [ZnTPP] 



Cone. (Mol/1) 



Time [THP] X [ZnTPP] X 

 (min) 102 10^ 



/(mm) 



ki (corr.) 

 1 mol-' 



kz 

 12 mol-2 



mm 



mm 



27.5 



26.6 



28.1 



27.1 

 27.1 

 28.0 

 28.4 

 25.9 

 25.2 

 25.5 



fci X 10^ 

 (mm 1^ mol~2) 



9.41 

 9.21 

 8.73 

 8.23 

 7.65 

 7.41 

 7.37 

 7.25 

 7.28 

 7.47 

 7.66 

 7.44 

 7.28 



Concentration and luminescence vs. time, smoothed data taken from curves of 

 Figs. 1 and 2. 



range studied, and is relatively independent of variations in the 

 initial concentration ratio of peroxide and catalyst (3, 9) . 



3. Spectra. Fig. 3 gives a comparison between the fluorescence 

 spectrum of ZnTPP, as excited at 148°C in ^butyl benzene by 436 

 niyu, mercury radiation, and the chemiluminescence spectrum at the 

 same temperature (Abrahamson) . It is seen that both emissions have 

 their maximum at 6506 A (neon spectrum) . A small high-energy 

 shoulder is also foimd in the fluorescence spectrum, which may be 

 due to a trace of impurity. A similar close correspondence between 

 fluorescence and chemiluminescence emission was found by Knorr and 

 Albers, using chlorophyll as catalyst (8) . 



4. Metal Requirement. Free tetraphenylporphine (TPP) has no 

 accelerating effect on the rate of THP breakdown, and shows no 



