Review and Analysis of Thermophysical Properties of a Sulfuric Acid–Water Electrolyte

Oca, Laura; Campillo-Robles, Jose Miguel; Bou-Ali, M. Mounir

doi:10.1021/acs.jced.8b00466

Cited by 6 publications

(8 citation statements)

References 64 publications

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“…where σ , ρ, and R v denote the surface tension, density, and the gas constant of water vapor, respectively. In CLaMS-Ice, the parameterizations for the surface tension σ and the density ρ are taken from Tabazadeh et al (2000) 4 and Oca et al (2018), respectively. Note that since the water activity depends on the amount x of sulfuric acid within the particle, it is also a function of the particle radius r with a w ∼ 1 r 3 (Wang, 2013;Petters and Kreidenweis, 2007).…”

Section: Fixing Carslaw's Methodsmentioning

confidence: 99%

New investigations on homogeneous ice nucleation: the effects of water activity and water saturation formulations

et al. 2022

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Abstract. Laboratory measurements at the AIDA cloud chamber and airborne in situ observations suggest that the homogeneous freezing thresholds at low temperatures are possibly higher than expected from the so-called “Koop line”. This finding is of importance, because the ice onset relative humidity affects the cirrus cloud coverage and, at the very low temperatures of the tropical tropopause layer, together with the number of ice crystals also the transport of water vapor into the stratosphere. Both the appearance of cirrus clouds and the amount of stratospheric water feed back to the radiative budget of the atmosphere. In order to explore the enhanced ice onset humidities, we re-examine the entire homogeneous ice nucleation process, ice onset, and nucleated crystal numbers, by means of a two-moment microphysics scheme embedded in the trajectory-based model (CLaMS-Ice) as follows: the well-understood and described theoretical framework of homogeneous ice nucleation includes certain formulations of the water activity of the freezing aerosol particles and the saturation vapor pressure of water with respect to liquid water. However, different formulations are available for both parameters. Here, we present extensive sensitivity simulations testing the influence of three different formulations for the water activity and four for the water saturation on homogeneous ice nucleation. We found that the number of nucleated ice crystals is almost independent of these formulations but is instead sensitive to the size distribution of the freezing aerosol particles. The ice onset humidities, also depending on the particle size, are however significantly affected by the choices of the water activity and water saturation, in particular at cold temperatures ≲205 K. From the CLaMS-Ice sensitivity simulations, we here provide combinations of water saturation and water activity formulations suitable to reproduce the new, enhanced freezing line.

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Section: Fixing Carslaw's Methodsmentioning

confidence: 99%

New investigations on homogeneous ice nucleation: the effects of water activity and water saturation formulations

et al. 2022

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“…The 17 O shift difference trend is remarkably linear across the concentration range, in contrast to the line-width trends (and indeed, the 33 S-shift trend), which exhibit increasingly greater curvature as the concentration is increased, with the onset at concentrations just above the deep eutectic point (∼4.5 M). The viscosity of aqueous H 2 SO 4 solutions begins to increase more sharply in this region with increasing concentrations, so the broadening is another manifestation of this reduction in solution dynamics. On the other hand, chemical shift is a reflection of the local electronic environment, so the smooth, linear trend in decreasing 17 O shift separation is an indication that the respective water and sulfate environments are increasingly mediated by proton exchange.…”

Section: Resultsmentioning

confidence: 97%

“…The line widths of both types of species exhibit the expected lowtemperature broadening, likely to be primarily induced by the increased viscosity under that condition, 41 but this broadening is considerably more significant for the solutions with concentrations above 5 M, which are noticeably more viscous when mixed even at room temperature. 29 Interestingly, the 17 O chemical shift difference is quite insensitive to temperature. Figure S4c illustrates the shift difference at a given temperature, Δ[δ( 17 O)](T), with the mean over all the examined temperatures at a given concentration subtracted off.…”

Section: Resultsmentioning

confidence: 99%

“…The solution structure of sulfuric acid influences its transport properties, which are essential to its performance as an electrolyte and have been well characterized through viscosity, , electrical conductivity, , optical diffusivity, , and gravimetric diffusivity measurements, and a combined Raman spectroscopy/model-based approach for diffusivity measurements . Analysis of the self-diffusivity of sulfuric acid solutions has been limited to the diffusion of solutes .…”

Section: Introductionmentioning

confidence: 99%

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Concentration-Dependent Solvation Structure and Dynamics of Aqueous Sulfuric Acid Using Multinuclear NMR and DFT

et al. 2021

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Sulfuric acid is a ubiquitous compound for industrial processes, and aqueous sulfate solutions also play a critical role as electrolytes for many prominent battery chemistries. While the thermodynamic literature on it is quite well-developed, comprehensive studies of the solvation structure, particularly molecular-scale dynamical and transport properties, are less available. This study applies a multinuclear nuclear magnetic resonance (NMR) approach to the elucidation of the solvation structure and dynamics over wide temperature (−10 to 50 °C) and concentration (0–18 M) ranges, combining the 17O shift, line width, and T 1 relaxation measurements, 33S shift and line width measurements, and 1H pulsed-field gradient NMR measurements of proton self-diffusivity. In conjunction, these results indicate a crossover between two regimes of solvation structure and dynamics, occurring above the concentration associated with the deep eutectic point (∼4.5 M), with the high-concentration regime dominated by a strong water–sulfate correlation. This description was borne out in detail by the activation energy trends with increasing concentration derived from the relaxation of both the H2O/H3O+ and H2SO4/HSO4 –/SO4 2– 17O resonances and the 1H self-diffusivity. However, the 17O chemical shift difference between the H2O/H3O+ and H2SO4/HSO4 –/SO4 2– resonances across the entire temperature range is nevertheless strikingly linear. A computational approach coupling molecular dynamics simulations and density functional theory NMR shift calculations to reproduce this trend is presented, which will be the subject of further development. This combination of multinuclear, dynamical NMR, and computational methods, and the results furnished by this study, will provide a platform for future studies on battery electrolytes where aqueous sulfate chemistry plays a central role in the solution structure.

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“…[6], and likely were derived from the same source; because they are redundant, they will not be included in our data set. There are a number of more recent measurements summarized in Oca et al [20], but these have not been pursued. One recent report from Los Alamos National Laboratory also measured densities between 7°C and 25°C [21], and these compare favorably with the other data at two temperatures in Figure 8.…”

Section: Densities Of H 2 So 4 Solutionsmentioning

confidence: 99%

Density Calculations of Actinide Solutions using the Pitzer Method

Weber

Hite

Alwin

2019

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Review and Analysis of Thermophysical Properties of a Sulfuric Acid–Water Electrolyte

Cited by 6 publications

References 64 publications

New investigations on homogeneous ice nucleation: the effects of water activity and water saturation formulations

New investigations on homogeneous ice nucleation: the effects of water activity and water saturation formulations

Concentration-Dependent Solvation Structure and Dynamics of Aqueous Sulfuric Acid Using Multinuclear NMR and DFT

Density Calculations of Actinide Solutions using the Pitzer Method

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