scholarly journals Predicting the Logarithmic Distribution Factors for Coprecipitation into an Organic Salt: Selection of Rare Earths into a Mixed Oxalate

Minerals ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 712
Author(s):  
Harry Watts ◽  
Yee-Kwong Leong

Thermodynamic modelling of a leaching system that involves concurrent precipitation depends on an understanding of how the metals distribute into the precipitate before an assessment of solubility can be made. It has been suggested in the past that a pair of rare earths (A and B) in solution will separate from each other by oxalate precipitation according to a logarithmic distribution coefficient (λ), determined by the kinetics of the precipitation. By contrast, the present study hypothesises that λ may be approximated from thermodynamic terms, including the solubility product (KSp) of each rare earth oxalate and the stability constant (β1) for the mono-oxalato complex of each rare earth. The proposed model was used to calculate λ between pairs of rare earths. An experimental study was conducted to determine λ between selected pairs using homogenous precipitation through the hydrolysis of an oxalic acid ester, with fairly close agreement to the values under the proposed model. Though this model requires more thorough testing, as well as application to other organic salts, it may provide insight into distribution factors of a precipitate formed by a sequence of organic complexes.

2013 ◽  
Vol 13 (11) ◽  
pp. 30653-30685
Author(s):  
G. Drozd ◽  
J. Woo ◽  
S. A. K. Häkkinen ◽  
A. Nenes ◽  
V. F. McNeill

Abstract. Volatility and hygroscopicity are two key properties of organic aerosol components, and both are strongly related to chemical identity. Here we show that inorganic-organic component interactions typically not considered in atmospheric models may strongly affect aerosol volatility and hygroscopicity. In particular, bi-dentate binding of di-carboxylic acids (DCA) to soluble inorganic ions can lead to very strongly bound metal-organic complexes with largely undetermined hygroscopicity and volatility. These reactions profoundly impact particle hygroscopicity, transforming hygroscopic components into irreversibly non-hygroscopic material. While the hygroscopicities of pure salts, DCA, and DCA salts are known, the hygroscopicity of internal mixtures of hygroscopic salts and DCA, as they are typically found in the atmosphere, has not been fully characterized. We have studied the volatility of pure, dry organic salt particles and the hygroscopicity of internal mixtures of oxalic acid (OxA, the dominant DCA in the atmosphere) and a number of salts, both mono- and di-valent. The formation of very low volatility organic salts was confirmed, with minimal evaporation of oxalate salt particles below 75 °C. Dramatic increases in the CCN activation diameter for particles with divalent salts (e.g. CaCl2) and relatively small particle mass fractions of OxA indicate that standard volume additivity rules for hygroscopicity do not apply. Thus small organic compounds with high O:C are capable of forming low volatility and very low hygroscopicity particles. Given current knowledge of the formation mechanisms of OxA and M-Ox salts, surface enrichment of insoluble M-Ox salts is expected. The resulting formation of an insoluble coating of metal-oxalate salts can explain low particle hygroscopicities. The formation of particles with a hard coating could offer an alternative explanation for observations of glass-like particles with very low viscosity.


2014 ◽  
Vol 14 (10) ◽  
pp. 5205-5215 ◽  
Author(s):  
G. Drozd ◽  
J. Woo ◽  
S. A. K. Häkkinen ◽  
A. Nenes ◽  
V. F. McNeill

Abstract. Volatility and hygroscopicity are two key properties of organic aerosol components, and both are strongly related to chemical identity. While the hygroscopicities of pure salts, di-carboxylic acids (DCA), and DCA salts are known, the hygroscopicity of internal mixtures of these components, as they are typically found in the atmosphere, has not been fully characterized. Here we show that inorganic–organic component interactions typically not considered in atmospheric models can lead to very strongly bound metal–organic complexes and greatly affect aerosol volatility and hygroscopicity; in particular, the bi-dentate binding of DCA to soluble inorganic ions. We have studied the volatility of pure, dry organic salt particles and the hygroscopicity of internal mixtures of oxalic acid (OxA, the dominant DCA in the atmosphere) and a number of salts, both mono- and di-valent. The formation of very low volatility organic salts was confirmed, with minimal evaporation of oxalate salt particles below 75 °C. Dramatic increases in the cloud condensation nuclei (CCN) activation diameter for particles with di-valent salts (e.g., CaCl2) and relatively small particle volume fractions of OxA indicate that standard volume additivity rules for hygroscopicity do not apply. Thus small organic compounds with high O : C ratios are capable of forming low-volatility and very low hygroscopicity particles. Given current knowledge of the formation mechanisms of OxA and M–Ox salts, surface enrichment of insoluble M–Ox salts is expected. The resulting formation of an insoluble coating of metal-oxalate salts can explain low-particle hygroscopicities. The formation of particles with a hard coating could offer an alternative explanation for observations of glass-like particles without the need for a phase transition.


2020 ◽  
Vol 05 ◽  
Author(s):  
Silas Santos ◽  
Orlando Rodrigues ◽  
Letícia Campos

Background: Innovation mission in materials science requires new approaches to form functional materials, wherein the concept of its formation begins in nano/micro scale. Rare earth oxides with general form (RE2O3; RE from La to Lu, including Sc and Y) exhibit particular proprieties, being used in a vast field of applications with high technological content since agriculture to astronomy. Despite of their applicability, there is a lack of studies on surface chemistry of rare earth oxides. Zeta potential determination provides key parameters to form smart materials by controlling interparticle forces, as well as their evolution during processing. This paper reports a study on zeta potential with emphasis for rare earth oxide nanoparticles. A brief overview on rare earths, as well as zeta potential, including sample preparation, measurement parameters, and the most common mistakes during this evaluation are reported. Methods: A brief overview on rare earths, including zeta potential, and interparticle forces are presented. A practical study on zeta potential of rare earth oxides - RE2O3 (RE as Y, Dy, Tm, Eu, and Ce) in aqueous media is reported. Moreover, sample preparation, measurement parameters, and common mistakes during this evaluation are discussed. Results: Potential zeta values depend on particle characteristics such as size, shape, density, and surface area. Besides, preparation of samples which involves electrolyte concentration and time for homogenization of suspensions are extremely valuable to get suitable results. Conclusion: Zeta potential evaluation provides key parameters to produce smart materials seeing that interparticle forces can be controlled. Even though zeta potential characterization is mature, investigations on rare earth oxides are very scarce. Therefore, this innovative paper is a valuable contribution on this field.


Author(s):  
Sophia Kalantzakos

In 2010, because of a geopolitical incident between China and Japan, seventeen elements of the periodic table known as rare earths became notorious overnight. An “unofficial” and temporary embargo of rare-earth shipments to Japan alerted the world to China’s near monopoly position on the production and export of these indispensable elements for high-tech, defense, and renewable energy sources. A few months before the geopolitical confrontation, China had chosen to substantially cut export quotas of rare earths. Both events sent shockwaves across the markets, and rare-earth prices skyrocketed, prompting reactions from industrial nations and industry itself. The rare-earth crisis is not a simple trade dispute, however. It also raises questions about China’s use of economic statecraft and the impacts of growing resource competition. A detailed and nuanced examination of the rare-earth crisis provides a significant and distinctive case study of resource competition and its spill-over geopolitical effects. It sheds light on the formulation, deployment, longevity, effectiveness, and, perhaps, shortsightedness of policy responses by other industrial nations, while also providing an example of how China might choose to employ instruments of economic statecraft in its rise to superpower status.


Minerals ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 20
Author(s):  
Deniz Talan ◽  
Qingqing Huang

The increasing industrial demand for rare earths requires new or alternative sources to be found. Within this context, there have been studies validating the technical feasibility of coal and coal byproducts as alternative sources for rare earth elements. Nonetheless, radioactive materials, such as thorium and uranium, are frequently seen in the rare earths’ mineralization, and causes environmental and health concerns. Consequently, there exists an urgent need to remove these radionuclides in order to produce high purity rare earths to diversify the supply chain, as well as maintain an environmentally-favorable extraction process for the surroundings. In this study, an experimental design was generated to examine the effect of zeolite particle size, feed solution pH, zeolite amount, and contact time of solid and aqueous phases on the removal of thorium and uranium from the solution. The best separation performance was achieved using 2.50 g of 12-µm zeolite sample at a pH value of 3 with a contact time of 2 h. Under these conditions, the adsorption recovery of rare earths, thorium, and uranium into the solid phase was found to be 20.43 wt%, 99.20 wt%, and 89.60 wt%, respectively. The Freundlich adsorption isotherm was determined to be the best-fit model, and the adsorption mechanism of rare earths and thorium was identified as multilayer physisorption. Further, the separation efficiency was assessed using the response surface methodology based on the development of a statistically significant model.


2001 ◽  
Vol 56 (5) ◽  
pp. 381-385
Author(s):  
Z. Akdeniz ◽  
M . Gaune-Escard ◽  
M. P. Tosi

Abstract We determine a model of the ionic interactions in RF3 compounds, where R is a rare-earth element in the series from La to Lu, by an analysis of data on the bond length and the vibrational mode frequencies of the PrF3, GdF3 and HoF3 molecular monomers. All RF3 monomers are predicted to have a pyramidal shape, displaying a progressive flattening of the molecular shape in parallel with the lanthanide contraction of the bond length. The vibrational frequencies of all monomers are calculated, the results being in good agreement with the data from infrared studies of matrix-isolated molecules. We also evaluate the geometrical structure and the vibrational spectrum of the La2F6 and Ce2F6 dimers, as a further test of the proposed model. -PACS 36.40.Wa (Charged clusters)


1985 ◽  
Vol 49 ◽  
Author(s):  
Martin Stutzmann ◽  
Warren B. Jackson ◽  
Chuang Chuang Tsai

AbstractThe dependence of the creation and the annealing of metastable dangling bonds in hydrogenated amorphous silicon on various material parameters will be discussed in the context of a recently proposed model. After a brief review of the kinetic behaviour governing defect creation and annealing in undoped a- Si:H, a number of special cases will be analyzed: the influence of alloying with O, N, C, and Ge, changes introduced by doping and compensation, and the role of mechanical stress. Finally, possibilities to increase the stability of a-Si:H based devices will be examined.


2011 ◽  
Vol 98 (3-4) ◽  
pp. 125-131 ◽  
Author(s):  
Tian Jun ◽  
Yin Jingqun ◽  
Chen kaihong ◽  
Rao Guohua ◽  
Jiang Mintao ◽  
...  

2014 ◽  
Vol 1010-1012 ◽  
pp. 928-933
Author(s):  
Ju Chi Kuang ◽  
Xiao Gang Chen ◽  
Min Hua Chen

The principle and methodology of effluent treatment by iron-carbon micro electrolysis were introduced in the paper. Then design of the orthogonal experiments for dyeing effluent treatment was formulated. Discussion of influences of related factors on effluent treatment followed. Results were got after the detailed analysis. Therefore, we deduced the mechanism that the cations of Transition Metal (TM) and rare earth (RE) assist of zero-valent irons catalyzing degradation of dyeing effluent. The mechanism is formed based on the following explanation. Cations of manganese and cobalt easily penetrate Fe0lattices, while Ce4+cations do it difficultly because of their larger radius. Thus Ce4+is weaker than both of Mn2+and Co2+for helping zero-valent irons to improve their activity. Furthermore, because the valence electron structure of Mn2+is more stable than that of Co2+, Mn2+is better for assisting zero-valent iron catalysis of degradation of dyeing effluent than Co2+. Therefore, ranking of influence for zero-valent iron catalysis activity from greatest to smallest is Mn2+, Co2+and Ce4+.


2016 ◽  
Vol 24 (01) ◽  
pp. 1550021 ◽  
Author(s):  
Heekyu Woo ◽  
Young S. Shin

In this paper, a new third-order approximation model for an acoustic-structure interaction problem is introduced. The new approximation model is designed to be an accurate and a stable model for predicting the response of a submerged structure. The proposed model is obtained by combining two lower order approximation models instead of using an operator matching method. The stability of this model is checked by a modal analysis. Finally, the approximation model is coupled to the spherical shell structure, and its performance is checked by a shock analysis.


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