Solubilities in aqueous solutions of the sodium salts of succinic and glutaric acid with and without ammonium sulfate
Introduction
Field measurements have shown that the major chemical components of aerosols in the free and upper troposphere (UT) include organic and inorganic compounds and mineral dust [1], [2], with the most abundant inorganic components being ammonium and sulfate [3]. With respect to the organic fraction, dicarboxylic acids (DCA) have been found in a range of environments, particularly for aerosols that have undergone chemical aging [4]. Both primary organic and secondary organic aerosols have been found to contain DCA [3], and their concentration in aerosols is increasing [5]. Field measurements have shown that succinic and glutaric acids are among the most abundant DCA in atmospheric aerosols [5], [6], [7]. Mineral dust has also been observed in aerosols, especially under acidic conditions, where mineral dust components can be reacted to the aqueous phase through chemical aging [8], [9] The aqueous phase chemistry of aerosols can be enhanced by metals at the surface or reacted into the aerosol interior [8], [10]. The presence of organics, metals, and metal salts have been shown to be present in large numbers of aerosols in field studies with sources of sea spray (Na, Mg) [4], [11], [12], [13], biomass burning (K) [14], [15], and mineral dusts and meteoritic material (Na, K, Ca, Fe) [1], [16], [17], [18], [19]. Metal ions can displace hydrogen ions from organic acids to form carboxylate salts in atmospheric aerosols as shown by field and lab studies [11], [13], [20], [21]. As an example, a particle that experienced UT temperatures or dry conditions and contained dissolved NaCl and succinic acid could undergo the following:where n equals one or two (corresponding to the number of acidic hydrogens present in the acid). According to recent studies the HCl product is highly volatile, and the organic salt will remain in the particle since it has a much lower vapor pressure [13], [20]. The sodium oxalate salt could precipitate when the particle experiences either cold or dry conditions in the atmosphere [21]. While the solubilities of NaHC4H4O4 and Na2C4H4O4 in water are well known [22], the impact of ammonium sulfate on solubility in solutions of the sodium succinates has not been investigated. The solubility of NaHC5H6O4 in water has not been previously investigated to our knowledge, and that of Na2C5H6O4 has only recently been investigated [23]. In both cases the effect of ammonium sulfate on solubility in water has not been investigated. In particular, salts other than the sodium oxalates and ammonium sulfate could form from these complex solutions of ions as has been found for similar systems in our lab [24], [25].
Section snippets
Sample preparation
Solutions studied in our experiments were made by mixing chemicals as listed in Table 1 with deionized water. All samples were made such that NaOH was in very slight excess. For NaHC4H4O4 and Na2C4H4O4 samples, 1.005 ± 0.004 and 2.004 ± 0.007 NaOH/H2C4H4O4 mole ratio solutions were made, respectively. For NaHC5H6O4 and Na2C5H6O4 samples, 1.001 ± 0.001 and 2.002 ± 0.003 NaOH/H2C5H6O4 mole ratio solutions were made, respectively. (Throughout this paper values reported as a ± b are mean values (a)
NaHC4H4O4/H2O
The solubility of NaHC4H4O4 in water has been known for some time and values appear in standard compilations [22], [35], though these are based on the work of Marshall and Bain [36]. Two crystals form from solution dependent on the concentration of the precipitating solution. For solutions with sodium hydrogen succinate concentration w ≤ 0.39 (where w is defined as mass fraction solute), NaHC4H4O4·3H2O is the stable solid. At concentrations of w ≥ 0.39 NaHC4H4O4, NaHC4H4O4 solid forms from
Discussion and atmospheric implications
The solubilities of the sodium salts of oxalic and malonic acid have previously been studied in our lab [24], [25]. In both of those cases, we determined the order of solubility to be H2A > Na2A > NaHA, where A represents the organic anion. In this work we find glutaric acid and its sodium salts follow the same pattern, whereas succinic acid and its sodium salts follow the reverse ordering. We have compared the data sets in Fig. 6 where we plot the various solubilities. As an example, if we
Conclusions
We have studied the solubility of the sodium salts of succinic and glutaric acids with and without ammonium sulfate present. As we have observed in other systems, we determined that the least soluble solids are most often not the organic sodium salts or ammonium sulfate, but rather a salt made up of the ions present, namely lecontite. This is a mineral that has been generally overlooked in the literature in terms of its presence in atmospheric aerosols. However, we have determined in this
Acknowledgements
We wish to thank Anastasiya Vinokur and Dr. Ilia Guzei at the University of Wisconsin-Madison for running and analyzing the X-ray crystallography experiments.
Funding
This work was supported by the National Science Foundation (USA) Atmospheric Chemistry Program (AGS-1361592)
Declaration of interests
None.
References (41)
- et al.
Substitution of chloride in sea-salt particles by inorganic and organic anions
J. Aerosol. Sci.
(1998) - et al.
Sulfate-coated dust particles in the free troposphere over Japan
Atmos. Res.
(2006) - et al.
Aerosol single particle composition at the Jungfraujoch
J. Aerosol Sci.
(2005) - et al.
The solubility measurements of sodium dicarboxylate salts; sodium oxalate, malonate, succinate, glutarate, and adipate in water from T = (279.15 to 358.15) K
J. Chem. Thermodyn.
(2009) - et al.
Solubility of oxalic, malonic, succinic, adipic, maleic, malic, citric, and tartaric-acids in water from 278.15-K to 338.15-K
J. Chem. Thermodyn.
(1987) - et al.
In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers
Science
(1998) - et al.
Aerosols that form subvisible cirrus at the tropical tropopause
Atmos. Chem. Phys.
(2010) - et al.
Atmospheric Chemistry and Physics: From Air Pollution to Climate Change
(1998) - et al.
Investigations of the diurnal cycle and mixing state of oxalic acid in individual particles in Asian aerosol outflow
Environ. Sci. Technol.
(2007) - et al.
A sub-decadal trend in diacids in atmospheric aerosols in eastern Asia
Atmos. Chem. Phys.
(2016)
The formation, properties and impact of secondary organic aerosol: current and emerging issues
Atmos. Chem. Phys.
Dicarboxylic acids, oxoacids, benzoic acid, α-dicarbonyls, WSOC, OC, and ions in spring aerosols from Okinawa Island in the western North Pacific Rim: size distributions and formation processes
Atmos. Chem. Phys.
Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust
Atmos. Chem. Phys.
Surface modification of mineral dust particles by sulphuric acid processing: implications for ice nucleation abilities
Atmos. Chem. Phys.
Enhanced role of transition metal ion catalysis during in-cloud oxidation of SO2
Science
Tropospheric chemistry of internally mixed sea salt and organic particles: Surprising reactivity of NaCl with weak organic acids
J. Geophys. Res.
A review of biomass burning emissions part II: intensive physical properties of biomass burning particles
Atmos. Chem. Phys.
Air quality impact physicochemical aging of biomass burning aerosols during the, San Diego Wildfires
Environ. Sci. Technol.
Single-particle mass spectrometry of tropospheric aerosol particles
J. Geophys. Res. Atmos.
Direct observations of the atmospheric processing of Asian mineral dust
Atmos. Chem. Phys.
Cited by (3)
Phase diagrams of aqueous solutions of the potassium salts of malonic, succinic, and glutaric acids
2021, Journal of Chemical ThermodynamicsCitation Excerpt :It seems likely then, that the amount of substance undergoing these transitions is small compared to the fraction of the sample involved in the eutectic and liquidus transitions. We previously studied solubilities in NaHC5H6O4/H2O [16] and glutaric acid/H2O [25] systems. The precipitating solid in the NaHC5H6O4/H2O system was identified as NaHC5H6O4·2H2O and has a polymeric crystal structure.
pH effect on the release of NH<inf>3</inf> from the internally mixed sodium succinate and ammonium sulfate aerosols
2020, Atmospheric EnvironmentCitation Excerpt :From water content as a function of RH showed in Fig. S1(c), the efflorescence RH (ERH) from 48.3% to 41.5% and deliquescence RH (DRH) at 81.7% are decided, which agree well with the previous data (Choi and Chan, 2002; Parsons et al., 2004; Prenni et al., 2003). The SS is an important organic salt, whose solubility in aqueous solutions (Beyer and Buttke, 2018) and droplets have been measured by vapor sorption analyzer (Ma et al., 2013) and EDB (Peng and Chan, 2001) and H-TDMA (Wu et al., 2011) and ATR-FTIR technologies (Gao et al., 2018; Peng and Chan, 2001). Our IR spectra of SS droplets during dehydration and hydration courses are presented in Fig. S2 (a) and (b).
Deliquescence Relative Humidity and Reversible Non-deliquescent Water Uptake in the Sodium Salts of Succinic Acid
2021, ACS Earth and Space Chemistry