Cluster Formation of Sulfuric Acid with Dimethylamine or Diamines and Detection with Chemical Ionization

Abstract:

Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to chemically ionize clusters for detection. In this study, we compare measured cluster concentrations formed by reacting sulfuric acid vapor with dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine) using nitrate and acetate ions. We show from flow reactor measurements that nitrate is unable to chemically ionize clusters with weak acidities. In addition, we vary the ion-molecule reaction time to probe the chemical ionization processes and lifetimes of ions composed of sulfuric acid and base molecules. We then model the neutral and ion cluster formation pathways, including chemical ionization, ion-induced clustering, and ion decomposition, to better identify which cluster types cannot be chemically ionized by nitrate. Our results show that sulfuric acid dimer with two diamines and sulfuric acid trimer with 2 or more base molecules cannot be chemical ionized by nitrate. We conclude that cluster concentrations measured with acetate CI gives a better representation of both cluster abundancies and their base content than nitrate CI.