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The binding stability of water molecules with MeCl +  and MeClO 4  +  ions has been studied by the electrospray ionisation mass spectrometry (ESI-MS). The Me ions studied were the typical transitionmetals (Me = Fe, Co, Ni, Cu, Zn, or Cd) and the typical alkaline-earth metals (Me = Mg, Ca, Sr, or Ba). The increasing voltagebetween the skimmer cones (referred to as the cone voltage) induced the abstraction of water molecules from MeCl +  and MeClO 4  +  ions. The binding stability of water molecules with MeCl +  and MeClO 4  +  ions has been correlated with the Me cation mass and with the heat capacity of hydration of Me cations. Moreover, the physicochemicalproperties of the ions studied have been compared by the cluster analysis and the principal component analysis of the experimentalcurves obtained for the [MeCl-H 2 O] +  and [MeClO 4 - n H 2 O] +  ions, where  n  is 1 or 2. Our results can be useful in examination of the ion dehydration process.

Water Molecule Coupling to MeCl + and MeClO 4 + Ions Studied by the Electrospray Ionisation Mass Spectrometry