Atmospheric pressure corona discharge (APCD) was applied to the ionization of volatile organic compounds. The mass spectra of analytes having aromatic, phenolic, anilinic, basic and aliphatic in nature were obtained by using vapor supply and liquid smear supply methods. The vapor supply method mainly gave protonated analytes [A+H]+ caused by proton transfer from hydronium ion H3O+, except for benzene, toluene and n-hexane that have lower proton affinity. The use of the liquid smear supply method resulted in the formation of molecular ion A·+ and/or dehydride analyte [A-H]+, according to the nature of analytes used. The formation of A·+ without fragment ions could be explained by the electron tunneling via high electric fields 108 V/m at the tip of the corona needle. The dehydride analytes [A-H]+ observed in the mass spectra of n-hexane, di- and tributylamines may be explained by the hydride abstraction from the alkyl chains by the hydronium ion. The hydronium ion can play the two-roles for analytes, i.e., the proton donor to form [A+H]+ and the hydride acceptor to form [A-H]+.
Keywords: ambient ionization; corona discharge; field ionization; hydronium ion.