Pseudo-first-order rate constant oxygen reactions

The kinetics and mechanism of oxygen transfer in the reaction of p-cyano-N,N-dimethylaniline N-oxide with the manganese(III) complex of the me50-tetrakis(2,6-dimethylphenyl)porphinato dianion have been investigated in the presence of imidazole.From the dependence of the pseudo first-order rate constants upon [ImH], and a knowledge of the equilibrium constants for imidazole ligation, second-order rate constants of = 3.3 x 10 s 2 = 5.53 s and —... 

Liquid phase oxidation reaction of acetaldehyde with Mn acetate catalyst can be considered as pseudo first order irreversible reaction with respect to oxygen, and the reaction occurred in liquid film. The value of kinetic constant as follow k/ = 6.64.10 exp(-12709/RT), k2 = 244.17 exp(-1.8/RT) and Lj = 3.11.10 exp(-13639/RT) m. kmor. s. The conversion can be increased by increasing gas flow rate and temperature, however the effect of impeller rotation on the conversion is not significant. The highest conversion 32.5% was obtained at the rotation speed of 900 rpm, temperature 55 C, and gas flow rate 10" m. s. The selectivity of acetic acid was affected by impeller rotation speed, gas flow rate and temperature. The highest selectivity of acetic acid was 70.5% at 500 rpm rotation speed, temperature of 55 C... 

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. 

Let X and Y be the molar concentrations of N02 and NO and Xa and Y0 be these concentrations in the inlet stream, respectively. Then, Z-X+Y is the total NOx concentration. Let Ay be the reaction rate constant of the soot-N02 oxidation reaction and k A and kB the forward and backward rate constants for the NO oxidation, respectively. For the case of constant oxygen concentration across the soot layer the forward reaction can be considered of pseudo-first order with a modified rate constant kA=k [02f5. 

The composition of the reaction mixture in the vessel will be maintained at a constant low conversion by continuous withdrawal of the product stream and a steady inflow of fresh o-xylene. Under these conditions the reaction rate is approximately independent of the o-xylene concentration and is pseudo first-order with respect to the dissolved oxygen concentration C0. 

---