Study of elementary reactions of combustion importance at elevated temperatures and pressures

The aim of the present study is to study the kinetics of elementary reactions of combustion importance at elevated temperatures and pressures. High pressure is encountered in many systems of practical importance such as internal combustion engines and rocket combustion chambers. Several reactions of OH, CH_3 and HO_2 radicals are studied. The pressure range covered in this study is 1 - 100 bar and the temperature range is 292 - 834 K. The experimental approach used is laser photolysis coupled to UV transient absorption spectroscopy. A unique high pressure heatable flow reactor is employed and a novel approach of direct introduction of liquid precursors using a high pressure syringe pump is developed in this study. Methyl radicals are produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals are generated in the reaction of electronically excited oxygen atoms O(^1D), produced in the photolysis of N_2O at 193.3 nm with H_2O. The reaction of O(^1D) and hydroxyl with H_2O_2 produce hydroperoxy radicals. Temporal profiles of CH_3 and HO_2 are recorded via absorption at 216.4 and 224 nm, using xenon arc lamp and a spectrograph, OH radicals are monitored via transient absorption of light from a dc discharge H_2O/Ar low pressure OH discharge lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor is determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The reactions studied are OH + OH --> products (k_{OH+OH}), CH_3 + OH --> products (k_{CH3+OH}), CH_3 + CH_3 --> products (k_{CH3 + CH3}), and CH_3 +HO_2 --> products (k_{CH3 + HO2}). The pressure dependent rate constant in the self-reaction of OH radical is parameterized using the Troe expression as k_{1b,inf,OH+OH} = (2.3 +/- 0.5)x10^{-11}(T/300)^{-0.5} cm^3molecule^{-1}s^{-1}, k_{1b,0,OH+OH} = [He] (1.4 +/- 0.5)x10^{-30}(T/300)^{-4.6+/-0.5} cm^3molecule^{-1}s^{-1}, Fc = 0.37. The V- shaped temperature dependence of disproportionation channel (k_{OH+OH->H2O+O}) based on combined current and previous studies in the temperature range of 233 - 2380 K is (5.1 exp(-T/190 K) + 0.30(T/300 K)^{1.73})x10^{-12} cm^3molecule^{-1}s^{-1}. The rate constant of the reaction of CH_3 and OH is determined as k_{CH3 + OH} = (1.20 +/- 0.20)x10^{-10}(T/300)^{-0.49} cm^3molecule^{-1}s^{-1} pressure independent over the 1 - 100 bar range. The rate constant of self reaction of CH_3+CH_3 is k_{CH3 + CH3} = 5.94x10^{-11} (T/300)^{0.31}cm^3molecule^{-1}s^{-1}. The reaction of methyl radicals with hydroperoxy radicals (CH_3+HO_2 -> products), is studied at 295 K and 1 bar (He). The rate constant is (3.7 +/- 1.8)x10^{-11} cm^3molecule^{-1}s^{-1} (295 K, 1 bar, He).

Name thesis:degree_name

Doctor of Philosophy in Chemistry - (Ph.D.)

Discipline thesis:degree_discipline

Chemistry and Environmental Science

Year

2013

Author dc:creator

• Sangwan, Manuvesh

Contributors dc:contributor

• Lev N. Krasnoperov
• Joseph W. Bozzelli
• Carol A. Venanzi

• Gas phase kinetics
• Laser photolysis
• UV spectroscopy
• Radical-radical reaction
• High pressure kinetics
• Elementary reactions study
• Chemistry

Repository record dc:identifier

https://digitalcommons.njit.edu/dissertations/379

OAI identifier oai:identifier

oai:digitalcommons.njit.edu:dissertations-1434