The collisional history of ionized molecules in a molecular beam mass spectrometric flame experiment is target of our present investigation. Measurements in a double imaging photoelectron photoion coincidence spectroscopy (i²PEPICO) were performed at the Swiss Light Source (SLS) of the Paul Scherrer Institute to use the ion imaging device for separating the molecular beam ions from rethermalized ions. This enables the precise composition study of the individual types of ions. Results show clearly for the OH radical that the complete signal is obtained from the molecular beam, while the signal from other combustion compounds features additional rethermalized molecules. As for OH radicals, the mole fraction is reduced by sampling effects and contact with the ionization vessel walls significantly. Consequently, this leads to signal loss and lower mole fractions, when using ionization cross sections for the quantification. To improve on this, a beam fraction (BF) factor is presented. The factor describes the ratio of the separated beam signal without rethermalized ions with the total ion signal, consisting of the mass to charge ratio from the molecular beam and additional rethermalized ions. Since the detected OH radicals are solely from the molecular beam, a new method of comparing two molecular beam alignments using the OH to H₂O signal ratio is presented. This method has a decent potential for the optimization of the quality of molecular beams. Finally, the separated beam signal (without the rethermalized ions) was used to determine mole fraction profiles for the OH radical using ionization cross sections. These profiles are in good agreement with model predictions of the USC-II and the Aramco Mech 2.0 mechanisms, while the total signal leads to factor of 12 smaller OH mole fractions.