The structure of three laminar premixed rich flames has been investigated: a pure methane flame and two methane flames doped by allene and propyne, respectively. The gases of the three flames contain 20.9% (molar) of methane and 33.4% of oxygen, corresponding to an equivalence ratio of 1.25 for the pure methane flame. In both doped flames, 2.49% Of C3H4 was added, corresponding to a ratio C3H4/CH4 Of 12% and an equivalence ratio of 1.55. The three flames have been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 36 cm/s at 333 K. The concentration profiles of stable species were measured by gas chromatography after sampling with a quartz microprobe. Quantified species included carbon monoxide and dioxide, methane, oxygen, hydrogen, ethane, ethylene, acetylene, propyne, allene, propene, propane, 1,2-butadiene, 1,3-butadiene, 1-butene, isobutene, 1-butyne, vinylacetylene, and benzene. The temperature was measured using a PtRh (6%)-PtRh (30%) thermocouple settled inside the enclosure and ranged from 700 K close to the burner up to 1850 K. In order to model these new results, some improvements have been made to a mechanism previously developed in our laboratory for the reactions of C-3-C-4 unsaturated hydrocarbons. The main reaction pathways of consumption of allene and propyne and of formation Of C-6 aromatic species have been derived from flow rate analyses. (c) 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.