Sensitized photo-redox reaction——Ⅶ.The Synthesis,FAB mass spectrum,stationary absorption,emission,transient absorption spectra,redox potential of dihydroxy-tin(Ⅳ)-mesoporphyrin dimethyl ester and its sensitized photo-reduction of methyl viologen

In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)～-0.84V,E_(1/2)^(ox)～ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)～-0.33 V, E(P/P-)～+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.

Ignition enhancement of ethylene/air by NO_x addition

Recently, non-equilibrium plasma assisted combustion （PAC） has been found to be promising in reducing the ignition delay time in hypersonic propulsion system. NO x produced by non-equilibrium plasma can react with intermediates during the fuel oxidation process and thereby has influence on the combustion process. In this study, the effects of NO x addition on the ignition process of both the homogeneous ethylene/air mixtures and the non-premixed diffusion layer are examined numerically. The detailed chemistry for ethylene oxidization together with the NO x sub-mechanism is included in the simulation. Reaction path analysis and sensitivity analysis are conducted to give a mechanistic interpretation for the ignition enhancement by NO x addition. It is found that for both the homogenous and non-premixed ignition processes at normal and elevated pressures, NO 2 addition has little influence on the ignition delay time while NO addition can significantly promote the ignition process. The ignition enhancement is found to be caused by the promotion in hydroxyl radical production which quickly oxidizes ethylene. The promotion in hydroxyl radical production by NO addition is achieved in two ways：one is the direct production of OH through the reaction HO2＋NO = NO2＋OH, and the other is the indirect production of OH through the reactions NO＋O2=NO2＋O and C2H4＋O = C2H3＋OH. Moreover, it is found that similar to the homogeneous ignition process, the acceleration of the diffusion layer ignition is also controlled by the reaction HO2＋NO = NO2＋OH.