Stratospheric positive ion chemistry of formaldehyde and methanol

The reactions of H3O+·nH2O ions with CH2O and CH3OH have been studied in flowing afterglow and flow drift reaction systems. Hydrated protonated formaldehyde, CH2OH+·nH2O, reacts with H2O to form H3O+ hydrates and CH2O for small n. Therefore protonated formaldehyde ions are not expected to have significant atmospheric concentrations. Methanol reacts rapidly with H3O+ ·nH2O ions for n = 0, 1, 2, and 3. The absence of protonated methanol ions in the atmosphere above 40 km, where H3O+ ·nH2O (n = 0, 1, 2, and 3) are observed to be the dominant ions, yields a useful upper limit on the atmospheric concentration of methanol.

[1]  R. Taft,et al.  Gas phase basicities and relative proton affinities of compounds between water and ammonia from pulsed ion cyclotron resonance thermal equilibriums measurements , 1977 .

[2]  D. Krankowsky,et al.  First mass spectrometric measurements of positive ions in the stratosphere , 1977, Nature.

[3]  P. Crutzen,et al.  Ion chemistry of chlorine compounds in the troposphere and stratosphere , 1976 .

[4]  M. A. Garrett,et al.  Clustering studies of the formaldehyde ion , 1976 .

[5]  Z. Karpas,et al.  Ion-Molecule chemistry in formaldehyde by ion cyclotron resonance mass spectrometry , 1975 .

[6]  R. Varney,et al.  Reaction rate constants in steady‐state hollow cathode discharges: N2 + H2O reactions , 1974 .

[7]  D. Albritton,et al.  Flow‐drift technique for ion mobility and ion‐molecule reaction rate constant measurements. I. Apparatus and mobility measurements , 1973 .

[8]  D. Albritton,et al.  Flow‐drift technique for ion mobility and ion‐molecule reaction rate constant measurements. III. Negative ion reactions of O− with CO, NO, H2, and D2 , 1973 .

[9]  D. Albritton,et al.  Flow‐drift technique for ion mobility and ion‐molecule reaction rate constant measurements. II. Positive ion reactions of N+, O+, and H2+ with O2 and O+ with N2 from thermal to [inverted lazy s]2 eV , 1973 .

[10]  R. Bolden,et al.  A flowing afterglow study of water vapour , 1972 .

[11]  C. J. Howard,et al.  Gas‐Phase Reaction Rates of Some Positive Ions with Water at 296°K , 1970 .

[12]  F. Fehsenfeld,et al.  Origin of water cluster ions in the D region , 1969 .

[13]  F. Fehsenfeld,et al.  Flowing Afterglow Measurements of Ion-Neutral Reactions , 1969 .

[14]  F. Fehsenfeld,et al.  Ion–Molecule Reaction Studies from 300° to 600°K in a Temperature‐Controlled Flowing Afterglow System , 1968 .