Abstract
Abstract. In order to study the growth/shrinking of a hygroscopic nanoparticle during hydration/dehydration in an atmosphere of water vapour, we have employed a thermodynamic approach proposed by Shchekin et al. (2008). This approach uses the mechanic and thermodynamic concept of disjoining pressure of thin films and allows, among others, the prediction of the humidity growth factor of both (i) a homogeneous solution droplet with completely dissolved residual core and (ii) a heterogeneous solution droplet with partially dissolved residual core as a function of the ambient relative humidity. For application to a nanometric sodium chloride particle we have extended the original approach by (i) considering the nonideality of the solution through the dependence of molecular volumes of the solvent and solute molecules and the solute and solvent activities on the solution concentration, (ii) deriving an equation for the estimation of the efflorescence properties of a homogeneous solution droplet, and (iii) combining the empirical power law fittings for the size dependence of the deliquescence and efflorescence relative humidity values by Biskos et al. (2006a). It was demonstrated how the solution/solute interface energy and the correlation length of a thin solution film can be determined from a combination of experimentally determinable efflorescence and deliquescence humidities with the present calculus. The solution/solute interface energy was found to be in close agreement with some previous values reported in the literature, while it strongly differs from data of some other sources. The calculated deliquescence humidity shows a low sensitivity to the choice of the numerical value for the film correlation length. The estimated film correlation length of 1 nm for a nanometric sodium chloride particle with dry particle radius of 5 nm was found to be reconcilable with available a priori estimates of the correlation length from the literature when the measurement uncertainty of the deliquescence humidity is considered. Considering the combination of an extensive calculus, a comprehensive set of thermophysical constraints, and independent measurements of the deliquescence and efflorescence humidities as functions of dry particle radius, the obtained values of the solution/solute interface energy and the correlation length are in close agreement with previous estimations. The humidification of sodium chloride particles in the initial hydration stages was found to be very sensitive to the specification of the disjoining pressure. The enhancement of the wettability of the particle surface leads to an earlier onset of hygroscopic growth.
Highlights
The importance of deliquescence and efflorescence for atmospheric models and processes, especially for climate models, originates from associated radiative effects
The subsequent calculations were performed at T = 298 K for a dry NaCl particle radius of RN = 5 nm, corresponding to DRH ≈ 81 %rh and efflorescence humidity (ERH) ≈ 47 %rh according to Eq (9)
In order to study the growth/shrinking of a hygroscopic nanoparticle during hydration/dehydration in a solvent vapour atmosphere, we have employed a thermodynamic theory proposed by Shchekin, Shabaev, and Rusanov which allows the prediction of the humidity growth factor of both (i) a homogeneous solution droplet with completely dissolved residual core and (ii) a heterogeneous solution droplet with partially dissolved residual core as a function of the ambient relative humidity
Summary
The importance of deliquescence and efflorescence (the notions of which will be explained below) for atmospheric models and processes, especially for climate models, originates from associated radiative effects (see Anonymous Referee, 2014, and references given therein to e.g. Cziczo and Abbatt, 1999, Oatis et al, 1998, Xu et al, 1998, Lohmann and Feichter, 2005, Khvorostyanov and Curry, 2014, Sects. 2.3, 2.5, 6.1, 11.1 therein). Using the thermodynamic theory of thin solution films developed by Shchekin et al (1993), Kuni et al (2001), Djikaev et al (2001a), Djikaev et al (2001b) and Djikaev (2002) based on the mechanical and thermodynamic concept of the disjoining pressure, Shchekin and Shabaev (2005), Shchekin and Rusanov (2008) and Shchekin et al (2008) derived, for the limit of ideality of the aqueous electrolyte solution, generalisations of the Gibbs–Kelvin–Köhler (GKK) equation of the theory of nucleation on soluble particles and of the Ostwald–Freundlich (OF) equation of the theory of solutions (hereafter called SSR theory according to the initials of the authors Shchekin, Shabaev, and Rusanov) These equations allow (i) the determination of the humidity growth factor of a hygroscopic particle as a function of ambient temperature, relative humidity, dry particle radius, and of different thermophysical and interfacial parameters of the system and (ii) the determination of the DRH. A comprehensive detailed outline of the calculus can be found in the Supplement
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