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Chemical ionization (CI) mass spectrometers are used tostudy atmospheric nucleation by detecting clusters produced by reactions ofsulfuric acid and various basic gases. These instruments typically usenitrate to deprotonate and thus chemically ionize the clusters. In thisstudy, we compare cluster concentrations measured using either nitrate oracetate. Clusters were formed in a flow reactor from vapors of sulfuric acidand dimethylamine, ethylene diamine, tetramethylethylene diamine, orbutanediamine (also known as putrescine). These comparisons show thatnitrate is unable to chemically ionize clusters with high base content. Inaddition, we vary the ion–molecule reaction time to probe ion processeswhich include proton-transfer, ion–molecule clustering, and decomposition ofions. Ion decomposition upon deprotonation by acetate/nitrate was observed.More studies are needed to quantify to what extent ion decomposition affectsobserved cluster content and concentrations, especially those chemicallyionized with acetate since it deprotonates more types of clusters thannitrate.  Model calculations of the neutral and ion cluster formation pathways arealso presented to better identify the cluster types that are not efficientlydeprotonated by nitrate. Comparison of model and measured clusters indicatethat sulfuric acid dimers with two diamines and sulfuric acid trimers with twoor more base molecules are not efficiently chemical ionized by nitrate. Weconclude that acetate CI provides better information on cluster abundanciesand their base content than nitrate CI

Chemical ionization of clusters formed from sulfuric acid and dimethylamine or diamines