Flash pyrolysis of polyethyleneglycol. Part 2: Kinetics determined by T-jump/FTIR spectroscopy

Journal Article · Tue Apr 01 04:00:00 EST 1997 · Combustion and Flame

DOI:https://doi.org/10.1016/S0010-2180(96)00123-X· OSTI ID:543402

Arisawa, H; Brill, T B ^[1]

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1. Univ. of Delaware, Newark, DE (United States). Dept. of Chemistry

The rate of formation of all quantified products from flash-pyrolysis of polyethyleneglycol having Mw = 2090 (PEG-2090) was determined using T-jump/FTIR spectroscopy. In the 370--550 C range and at 2 atm Ar, a discontinuity in the Arrhenius plot occurs at 460--470 C. Below this temperature, E{sub a} = 7 {+-} 8 kcal/mol and In(A/s) = 1 {+-} 6. Above this temperature, E{sub a} = 22 {+-} 4 kcal/mol and In(A/s) = 12 {+-} 3. The explanation for this discontinuity lies in the fact that pyrolysis of PEG-2090 forms both volatile products and a higher Mw residue below the transition temperature. Above the transition temperature, pyrolysis products from both the PEG-2090 and the residue are formed. In addition to global kinetics, the kinetics of formation of the individual products were analyzed separately. For both the global process kinetics and the kinetics for formation of individual species (except for 2-methoxy-1,3-dioxolane below 460 C), the rate of desorption/evaporation controls the rate of release of species to the gas phase. At 11 atm, the global Arrhenius parameters for the formation of the products are E{sub a} = 52 {+-} 0.3 kcal/mol and In(A/s) = 32 {+-} 0.2 over the 400--550 C range, with no discontinuity. Thus, condensed-phase reactions dominate in controlling the product evolution rate at 11 atm.

• OSTI ID: 543402
• Journal Information: Combustion and Flame, Journal Name: Combustion and Flame Journal Issue: 1-2 Vol. 109; ISSN CBFMAO; ISSN 0010-2180
• Country of Publication: United States
• Language: English

Related Subjects

09 BIOMASS FUELS
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
ABSORPTION SPECTROSCOPY
CHEMICAL REACTION KINETICS
FLASH HEATING
FOURIER TRANSFORMATION
MOLECULAR WEIGHT
MUNICIPAL WASTES
POLYETHYLENE GLYCOLS
PYROLYSIS
PYROLYSIS PRODUCTS