Rate constants chemiluminescence

The first detailed investigation of the reaction kinetics was reported in 1984 (68). The reaction of bis(pentachlorophenyl) oxalate [1173-75-7] (PCPO) and hydrogen peroxide cataly2ed by sodium saUcylate in chlorobenzene produced chemiluminescence from diphenylamine (DPA) as a simple time—intensity profile from which a chemiluminescence decay rate constant could be determined. These studies demonstrated a first-order dependence for both PCPO and hydrogen peroxide and a zero-order dependence on the fluorescer in accord with an earher study (9). Furthermore, the chemiluminescence quantum efficiencies Qc) are dependent on the ease of oxidation of the fluorescer, an unstable, short-hved intermediate (r = 0.5 /is) serves as the chemical activator, and such a short-hved species "is not consistent with attempts to identify a relatively stable dioxetane as the intermediate" (68). 

Decomposition of diphenoylperoxide [6109-04-2] (40) in the presence of a fluorescer such as perylene in methylene chloride at 24°C produces chemiluminescence matching the fluorescence spectmm of the fluorescer with perylene was reported to be 10 5% (135). The reaction follows pseudo-first-order kinetics with the observed rate constant increasing with fluorescer concentration according to = k [flr]. Thus the fluorescer acts as a catalyst for peroxide decomposition, with catalytic decomposition competing with spontaneous thermal decomposition. An electron-transfer mechanism has been proposed (135). 

Vichutinsky, "Chemiluminescent Methods for the Determination of the Absolute Magnitude of the Termination Rate Constants of Peroxide Radicals in the Liquid Phase , PA Tech Translation 66(1967) 17) R. Czerepinski G.H. 

This model permits a determination of the rate constants for the rise of the chemiluminescence intensity and its subsequent decay and, more importantly, allows a quantitative assessment of the effects of reaction conditions, such as solvent variation, temperature, or additives, on the rates (r and f), the time required (t... 

Figure 13, indicates that the first mole of phenol is released in <30 s, the same elapsed time for the chemiluminescence to reach a maximum intensity. In fact, the measured rate constant r, for the rise in the chemiluminescence emission, is identical to the rate of the first phenol s release from the oxalate ester. Furthermore, the slower rate of release of the second phenol ligand has a rate constant that is identical to the chemiluminescence decay rate f. Thus, the model allows a quantitative analysis of the reaction mechanism, heretofore not available to us. We intend to continue this avenue of investigation in order to optimize the chemiluminescence efficiencies under HPLC conditions and to delineate further the mechanism for peroxy-oxalate chemiluminescence. 

Recently, we have shown that non-isothermal chemiluminescence measurements for oxidized cellulose provide the same rate constants of cellulose degradation as may be measured from experiments on the decay of polymerization degree determined by viscometry. This may be also taken as indirect evidence that the light emission is somehow linked with the scission of polymer chains [29]. 

The rate constant k, which involves the rate constant of bimolecular decomposition of hydroperoxides khi from the Scheme 2 may thus be determined, so that we find the value of [d(f/Imax)/df], which is the slope of chemiluminescence-time record at its inflexion point. This ratio is function of k as follows ... 

Table 3 The rate constants k determined from chemiluminescence experiments of Figure 15 and Equation (14) and the rate constants k of decomposition of hydroperoxides from literature... 

The difference between the chemiluminescence response of polyisoprene and cellulose on jump changes of atmosphere from nitrogen to oxygen (cf. Figure 16 and Figure 17) is probably due to the fact that the rate constant /y < 4 for... 

The effect of oxygen concentration is thus included in a constant m, which modifies both the resulting maximum of the chemiluminescence intensity and the apparent rate constant k of hydroperoxide decomposition. 

CL reactions are commonly divided into two classes. In the type I (direct) reaction the oxidant and reductant interact with rate constant kr to directly form the excited product whose excited singlet state decays with the first (or pseudofirst)-order rate constant ks = kf+ kd. In the type II (indirect) reaction the oxidant and reactant interact with the formation of an initially excited product (kr) followed by the formation of an excited secondary product, either by subsequent chemical reaction or by energy transfer, with rate constant kA. The secondary product then decays from the lowest excited singlet state with rate constant kt. Type II reactions are generally denoted as complex or sensitized chemiluminescence. 

Chemiluminescence is believed to arise from the 2Bj and the 2B2 electronic states, as discussed above for the reaction of NO with ozone [17]. The primary emission is in a continuum in the range =400-1400 nm, with a maximum at =615 nm at 1 torr. This emission is significantly blue-shifted with respect to chemiluminescence in the NO + 03 reaction (Xmax = 1200 nm), as shown in Figure 2, owing to the greater exothermicity available to excite the N02 product [52], At pressures above approximately 1 torr of 02, the chemiluminescence reaction becomes independent of pressure with a second-order rate coefficient of 6.4 X 10 17 cm3 molec-1 s-1. At lower pressures, however, this rate constant decreases and then levels off at a minimum of 4.2 X 1(T18 cm3 molec-1 s-1 near 1 mtorr, and the emission maximum blue shifts to =560 nm [52], These results are consistent with the above mechanism in which the fractional contribution of (N02 ) to the emission spectrum increases as the pressure is decreased, therefore decreasing the rate at which (N02 ) is deactivated to form N02. Additionally, the radiative lifetime and emission spectrum of excited-state N02 vary with pressure, as discussed above for the NO + 03 reaction [19-22],... 

In this case, chemiluminescence was monitored using a red-sensitive PMT to detect emissions from HFf. A factor-of-six enhancement in sensitivity to 1.1 parts per billion (ppbv) DMS was obtained. This is consistent with the fact that, based on the rate constant for the H + F2 rate determining step [Reaction (28)], the reaction can cycle approximately 7 times during the cell residence time and confirms the observation by Turnipseed and Birks [7] that F atoms are produced in the F2 + DMS reaction. 

Rate Constants for Reaction of Peroxyl Radical ROO with Flavonoids and Related Compounds (Kinetic Chemiluminescence Experiments) [102]... 

Ozone decay was measured in an office, a home, and several metal test facilities. Measurements were carried out with a Mast ozone meter and an MEC chemiluminescence ozone detector. The latter was calibrated with a stable ozone source and the epa neutral buffered potasaum iodide procedure. (It was noted over a wide range of concentrations that the mec meter measurements were consistently higher than those of the Mast meter by a factor of 1.3. That this is essentially identical with the findings of the DeMore committee is interesting.) Ozone generated by a positive corona ionizer was introduced into the test facilities. Ozone decay in a metal-walled room was found to be first-order, with the rate constant... 

Finally, in activated chemiluminescence, an added compound also leads to an enhancement of the emission intensity however, in contrast with the indirect CL, this compound, now called activator (ACT), is directly involved in the excitation process and not just excited by an energy transfer process from a formerly generated excited product (Scheme 5). Activated CL should be considered in two distinct cases. In the first case, it involves the reaction of an isolated HEI, such as 1,2-dioxetanone (2), and the occurrence of a direct interaction of the ACT with this peroxide can be deduced from the kinetics of the transformation. The observed rate constant (kobs) in peroxide decomposition is expected to increase in the presence of the ACT and a hnear dependence of kobs on the ACT concentration is observed experimentally. The rate constant for the interaction of ACT with peroxide ( 2) is obtained from the inclination of the linear correlation between obs and the ACT concentration and the intercept gives the rate constant for the unimolec-ular decomposition ( 1) of this peroxide (Scheme 5). The emission observed in every case is the fluorescence of the singlet excited ACT" ° . ... 

An indirect method has been used to determine relative rate constants for the excitation step in peroxyoxalate CL from the imidazole (IM-H)-catalyzed reaction of bis(2,4,6-trichlorophenyl) oxalate (TCPO) with hydrogen peroxide in the presence of various ACTs . In this case, the HEI is formed in slow reaction steps and its interaction with the ACT is not observed kinetically. However, application of the steady-state approximation to the reduced kinetic scheme for this transformation (Scheme 6) leads to a linear relationship of l/direct measure of the rate constant of the excitation step. 

Rauhut and coworkers were the first to obtain rate constants from emission kinetic studies and to verify the dependence of kobsi and kobsi on the concentration of the base catalyst and on hydrogen peroxide, respectively. Schowen and coworkers , using TCPO, H2O2 and DPA, with triethylamine as catalyst, observed an oscillatory behavior in emission experiments and proposed a mechanism involving the formation of two HEIs (involved in parallel chemiluminescent reactions) to explain it. Other authors have also observed a similar oscillating behavior but have explained it as a complex... 

The peroxyoxalate system is the only intermolecular chemiluminescent reaction presumably involving the (71EEL sequence (Scheme 44), which shows high singlet excitation yields (4>s), as confirmed independently by several authors Moreover, Stevani and coworkers reported a correlation between the singlet quantum yields, extrapolated to infinite activator concentrations (4> ), and the free energy involved in back electron-transfer (AG bet), as well as between the catalytic electron-transfer/deactivation rate constants ratio, ln( cAx( i3), and E j2° (see Section V). A linear correlation of ln( cAx( i3) and E /2° was obtained for the peroxyoxalate reaction with TCPO and H2O2 catalyzed by imidazole and for the imidazole-catalyzed reaction of 57, both in the presence of five activators commonly used in CIEEL studies (anthracene, DPA, PPO, perylene and rubrene). A further confirmation of the validity of the CIEEL mechanism in the excitation step of... 

Free energy, chemiluminescence rate constants, 1234 Free radicals... 

The rate constants for recombination of radicals, k, were determined using the chemiluminescence method, which consists in recording the intensity of luminescence induced by recombination of R02 radicals, when the system passes from one steady state to another (6). A change in steady state was induced by introducing an initiator (Figure 1). The k6 value was obtained from... 

When oxygen is removed from a reaction solution of tetrakis-(dimethylamino)ethylene (TMAE), the chemiluminescence decays slowly enough to permit rate studies. The decay rate constant is pseudo-first-order and depends upon TMAE and 1-octanol concentrations. The kinetics of decay fit the mechanism proposed earlier for the steady-state reaction. The elementary rate constant for the dimerization of TMAE with TMAE2+ is obtained. This dimerization catalyzes the decomposition of the autoxidation intermediate. 

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