New ignition delay time measurements of natural gas mixtures enriched with small amounts of n-hexane and n-heptane were performed in a rapid compression machine to interpret the sensitization effect of heavier hydrocarbons on auto-ignition at gas-turbine relevant conditions. The experimental data of natural gas mixtures containing alkanes from methane to n-heptane were carried out over a wide range of temperatures (840–1050 K), pressures (20–30 bar), and equivalence ratios (φ = 0.5 and 1.5). The experiments were complimented with numerical simulations using a detailed kinetic model developed to investigate the effect of n-hexane and n-heptane additions. Model predictions show that the addition of even small amounts (1–2%) of n-hexane and n-heptane can lead to an increase in reactivity by ∼40–60 ms at compressed temperature (TC) = 700 K. The ignition delay time (IDT) of these mixtures decreases rapidly with an increase in concentration of up to 7.5% but becomes almost independent of the C6/C7 concentration beyond 10%. This sensitization effect of C6 and C7 is also found to be more pronounced in the temperature range 700–900 K compared to that at higher temperatures (>900 K). The reason is attributed to the dependence of IDT primarily on H2O2(+M) ↔ 2ȮH(+M) at higher temperatures while the fuel-dependent reactions such as H-atom abstraction, RȮ2 dissociation, or Q˙
OOH + O2 reactions are less important compared to 700–900 K, where they are very important.