Burning velocities of R-32/O2/N2 mixtures: Experimental measurements and development of a validated detailed chemical kinetic model

This work entails characterizing the flammability of the refrigerant R-32 (CH2F2) by both experimental measurements and modeling. Burning velocities S u were measured using a constant-volume spherical-flame method for R-32/O-2/N-2 mixtures with O-2/N-2 ratios ranging from 21% (synthetic air) to 40%, pressures of (1 to 3) bar, and equivalence ratios phi of (0.8 to 1.3). Based on a critical assessment of available data, and extended by our own calculations, a detailed chemical kinetic model was developed and key reactions determined using reaction path and sensitivity analyses. Initiation and combustion were identified as distinct kinetic regimes and burning velocities were found to be controlled by two primary reactions: unimolecular decomposition of CH2F2 -> CHF + HF and the subsequent reaction, CHF + O-2 -> CHFO + O, the latter reaction initiating the radical chain propagating and branching by producing O atoms. Sensitive rate constants in the kinetic model were critically adjusted within their uncertainties and current knowledge bounds to best fit the experimental burning velocities. We found that rate constants in the model could be adjusted to match a given experimental S-u for specific conditions (O-2 loading, P, T, phi). This, however, then fixes predicted burning velocities for other all conditions within (3 to 4)% if physically realistic rate parameters are maintained. Thus, the entire set of experimental data is fit, not just to particular conditions. Relative random uncertainties in the experimental S-u measurements were (4 to 6)%, but assumptions made for thermal radiation lost by the burned gas in the spherical-flame experiments add an additional systematic uncertainty. Systematic differences between the limiting cases of adiabatic (no thermal radiation lost) and optically-thin (all thermal radiation lost) varied significantly with conditions and ranged from (4 to 30)% at high to low velocities, respectively, translating into uncertainties of (2 to 15)% considering the average of two limiting cases. Comparison of experimental and kinetically modeled S-u values suggests that the burned gas tends towards the optically-thin limit at the lowest pressures and fuel loadings and toward the adiabatic limit at the highest pressures and loadings. We tested and found support for this conclusion with a detailed analysis as a function of all the conditions (T, P, % O-2, phi). This behavior appears to transition from optically-thin to adiabatic as the density of the initial fuel increases, which results in increased CO2 in the burned gas and thus increased absorption of the thermal radiation (consistent with the Beer-Lambert Law). The validated detailed model based on evaluated kinetics is shown to accurately predict burning velocities for R-32 O-2/N-2 mixtures over a wide range of conditions and provides a reliable basis for extrapolation to other conditions. Published by Elsevier Inc. on behalf of The Combustion Institute.

Automated summary

This work characterizes the flammability of refrigerant R-32 through experimental measurements and modeling, showing that burning velocities are controlled by key reactions and can be adjusted in the kinetic model to fit experimental data. The study found systematic uncertainties in measurements and differences between adiabatic and optically-thin limits, with burning velocities transitioning between these limits depending on various conditions. The validated detailed model accurately predicts burning velocities for R-32 mixtures under different conditions, providing a reliable basis for extrapolation.