References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-8735-2011

Amine reactivity with charged sulfuric acid clusters

Bzdek

B. R.

¹ Ridge

D. P.

¹ Johnston

M. V.

Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, USA

26 08 2011

11 16 8735 8743

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The distribution of charged species produced by electrospray of an ammonium sulfate solution in both positive and negative polarities is examined using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Positively-charged ammonium bisulfate cluster composition differs significantly from negatively-charged cluster composition. For positively-charged clusters all sulfuric acid is neutralized to bisulfate, whereas for negatively-charged clusters the degree of sulfuric acid neutralization is cluster size-dependent. With increasing cluster size (and, therefore, a decreasing role of charge), both positively- and negatively-charged cluster compositions converge toward ammonium bisulfate. The reactivity of negatively-charged sulfuric acid-ammonia clusters with dimethylamine and ammonia is also investigated by FTICR-MS. Two series of negatively-charged clusters are investigated: [(HSO4)(H2SO4)x]− and [(NH4)x(HSO4)x+1(H2SO4)3]−. Dimethylamine substitution for ammonia in [(NH4) x(HSO4) x+1(H2SO4)3]− clusters is nearly collision-limited, and subsequent addition of dimethylamine to neutralize H2SO4 to bisulfate is within one order of magnitude of the substitution rate. Dimethylamine addition to [(HSO4) (H2SO4) x]− clusters is either not observed or very slow. The results of this study indicate that amine chemistry will be evident and important only in large ambient negative ions (>m/z 400), whereas amine chemistry may be evident in small ambient positive ions. Addition of ammonia to unneutralized clusters occurs at a rate that is ~2–3 orders of magnitude slower than incorporation of dimethylamine either by substitution or addition. Therefore, in locations where amine levels are within a few orders of magnitude of ammonia levels, amine chemistry may compete favorably with ammonia chemistry.

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