Strong Acids or Bases Displaced by Weak Acids or Bases in Aerosols: Reactions Driven by the Continuous Partitioning of Volatile Products into the Gas Phase.

Abstract

ConspectusAerosols are ubiquitous in the atmosphere and profoundly affect climate systems and human health. To gain more insights on their broad impacts, we need to comprehensively understand the fundamental properties of atmospheric aerosols. Since aerosols are multiphase, a dispersion of condensed matter (solid particles or liquid droplets, hereafter particles) in gas, partitioning of volatile matter between the condensed and the gas phases is one defining characteristic of aerosols. For example, water content partitioning under different relative humidity conditions, known as aerosol hygroscopicity, has been extensively investigated in the past decades. Meanwhile, partitioning of volatile organic or inorganic components, which is referred to as aerosol volatility, remains understudied. Commonly, a bulk solution system is treated as a single phase, with volatility mainly determined by the nature of its components, and the composition partitioning between solution and gas phase is limited. Aerosols, however, comprise an extensive gas phase, and their volatility can also be induced by component reactions. These reactions occurring within aerosols are driven by the formation of volatile products and their continuous partitioning into the gas phase. As a consequence, the overall aerosol systems exhibit prominent volatility. Noteworthily, such volatility induced by reactions is a phenomenon exclusively observed in the multiphase aerosol systems, and it is trivial in bulk solutions due to the limited extent of liquid-gas partitioning. Take the chloride depletion in sea salt particles as an example. Recent findings have revealed that chloride depletion can be caused by reactions between NaCl and weak organic acids, which release HCl into the gas phase. Such a reaction can be described as a strong acid displaced by a weak acid, which is hardly observed in bulk phase. Generally, this unique partitioning behavior of aerosol systems and its potential to alter aerosol composition, size, reactivity, and other physicochemical properties merits more attention by atmospheric community.This Account focuses on the recent advancements in the research of component reactions that induce aerosol volatility. These reactions can be categorized into four types: chloride depletion, nitrate depletion, ammonium depletion, and salt hydrolysis. The depletion of chloride or nitrate can be regarded as a displacement reaction, in which a strong acid is displaced by a weak acid. Such a reaction releases highly volatile HCl or HNO3 into the gas phase and leads to a loss of chloride or nitrate within the particles. Likewise, ammonium depletion is a displacement reaction in which a strong base is displaced by a weak base, resulting in release of ammonia and substantial changes in aerosol hygroscopicity. In addition, aerosol volatility can also be induced by salt hydrolysis in a specific case, which is sustained by the coexistence of proton acceptor and hydroxide ion acceptor within particles. Furthermore, we quantitatively discuss these displacement reactions from both thermodynamic and kinetic perspectives, by using the extended aerosol inorganic model (E-AIM) and Maxwell steady-state diffusive mass transfer equation, respectively. Given the ubiquity of component partitioning in aerosol systems, our discussion may provide a new perspective on the underlying mechanisms of aerosol aging and relevant climate effects.