Often, studies of microdroplet chemistry using electro-spray ionization mass spectrometry (MS) either find a negligible effect of the heated inlet capillary of the mass spectrometer on the reaction rate or do not consider its effect. In this context, we studied two reactions in microdroplets, the Pomeranz-Fritsch synthesis of isoquinoline and the Combes quinoline synthesis. The reagents were electrosprayed with methanol and aqueous solutions forming small and large microdroplets at flow rates of 1 and 20 mu L/min, respectively. We also varied the inlet capillary temperature from 100 to 350 degrees C. Contrary to the view that the inlet temperature has little to no influence on the reaction rate, we found that the Pomeranz-Fritsch reaction was markedly accelerated for both solvents and for both droplet sizes on increasing the temperature, whereas the Combes synthesis showed the opposite behavior. We propose that these strikingly different behaviors result from a competition of two effects, the evaporative cooling versus the heating of ejected bare ions from the droplet, both taking place inside the heated inlet. This finding suggests that these phenomena must be taken into account while interpreting the microdroplet reactions studied by electrospray or a similar kind of ambient ionization MS.