Differences in the reactivity of ammonium salts with methylamine
Abstract. The heterogeneous uptake of methylamine (MA) onto (NH4)2SO4, NH4HSO4, NH4NO3 and NH4Cl was investigated using a Knudsen cell reactor coupled to a quadrupole mass spectrometer, in situ Raman spectrometer and theoretical calculations. Exchange reactions were observed between MA and NH4NO3, (NH4)2SO4, and NH4Cl were observed at 298 K. Simple acid-base reaction for MA was found taking place on NH4HSO4. CH3NH3NO3 and CH3NH3Cl are not stable at low pressure and have higher dissociation vapor pressure than methylammonium sulfate. The observed uptake coefficients of MA on (NH4)2SO4, NH4HSO4, NH4NO3 and NH4Cl at 298 K were measured to be 6.30±1.03×10−3, 1.78±0.36×10−2, 8.79±1.99×10−3 and 2.29±0.28×10−3, respectively. A linear free energy relationship was found for the heterogeneous reactions between MA and NH4Cl, (NH4)2SO4 and NH4NO3. Namely, the natural logarithm of uptake coefficients of MA on these ammonium salts is linearly related to the electrostatic potential of the H atom in the NH4+ group.
