Comprehensive Analytical Modelling of an Absolute pH Sensor

In this work, we present a comprehensive analytical model and results for an absolute pH sensor. Our work aims to address critical scientific issues such as: (1) the impact of the oxide degradation (sensing interface deterioration) on the sensor’s performance and (2) how to achieve a measurement of the absolute ion activity. The methods described here are based on analytical equations which we have derived and implemented in MATLAB code to execute the numerical experiments. The main results of our work show that the depletion width of the sensors is strongly influenced by the pH and the variations of the same depletion width as a function of the pH is significantly smaller for hafnium dioxide in comparison to silicon dioxide. We propose a method to determine the absolute pH using a dual capacitance system, which can be mapped to unequivocally determine the acidity. We compare the impact of degradation in two materials: SiO2 and HfO2, and we illustrate the acidity determination with the functioning of a dual device with SiO2.

Assessing the level of confidence for expressing extended uncertainty: a model based on control errors in the measurement of ion activity

<p>A method for estimating the level of confidence when determining the coverage factor based on control errors is proposed, using the example of measurements of ion activity. Using information on tolerances and uncertainty, it is possible to establish a reasonable interval around the measurement result, within which most of the values that can be justified are assigned to the measured value.</p>

Pb Mineral Precipitation in Solutions of Sulfate, Carbonate and Phosphate: Measured and Modeled Pb Solubility and Pb2+ Activity

Lead (Pb) solubility is commonly limited by dissolution–precipitation reactions of secondary mineral phases in contaminated soils and water. In the research described here, Pb solubility and free Pb2+ ion activities were measured following the precipitation of Pb minerals from aqueous solutions containing sulfate or carbonate in a 1:5 mole ratio in the absence and presence of phosphate over the pH range 4.0–9.0. Using X-ray diffraction and Fourier-transform infrared spectroscopic analysis, we identified anglesite formed in sulfate-containing solutions at low pH. At higher pH, Pb carbonate and carbonate-sulfate minerals, hydrocerussite and leadhillite, were formed in preference to anglesite. Precipitates formed in the Pb-carbonate systems over the pH range of 6 to 9 were composed of cerussite and hydrocerussite, with the latter favored only at the highest pH investigated. The addition of phosphate into the Pb-sulfate and Pb-carbonate systems resulted in the precipitation of Pb3(PO4)2 and structurally related pyromorphite minerals and prevented Pb sulfate and carbonate mineral formation. Phosphate increased the efficiency of Pb removal from solution and decreased free Pb2+ ion activity, causing over 99.9% of Pb to be precipitated. Free Pb2+ ion activities measured using the ion-selective electrode revealed lower values than predicted from thermodynamic constants, indicating that the precipitated minerals may have lower KSP values than generally reported in thermodynamic databases. Conversely, dissolved Pb was frequently greater than predicted based on a speciation model using accepted thermodynamic constants for Pb ion-pair formation in solution. The tendency of the thermodynamic models to underestimate Pb solubility while overestimating free Pb2+ activity in these systems, at least in the higher pH range, indicates that soluble Pb ion-pair formation constants and KSP values need correction in the models.

Dissolution, Solubility, and Stability of the Basic Ferric Sulfate-Arsenates [Fe(SO4)x(AsO4)y(OH)z·nH2O] at 25–45°C and pH 2–10

Basic ferric sulfate-arsenates [FeSAsOH, Fe(SO4)x(AsO4)y(OH)z·nH2O] were prepared and characterized to study their potential fixation of arsenic in the oxidizing and acidic environment through a dissolution for 330d. The synthetic solids were well-shaped monoclinic prismatic crystals. For the dissolution of the sample FeSAsOH–1 [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O] at 25–45°C and initial pH 2, all constituents preferred to be dissolved in the order of AsO43− > SO42− > Fe3+ in 1–3 h, in the order of SO42− > AsO43− > Fe3+ from 1–3 h to 12–24 h, and finally in the order of SO42− > Fe3+ > AsO43−. The released iron, sulfate, and arsenate existed dominantly as Fe3+/Fe(OH)2+/FeSO4+, HSO4−/SO42−/FeSO4+, and H3AsO40/H2AsO4−, respectively. The higher initial pHs (6 and 10) could obviously inhibit the release of Fe3+ from solid into solution, and the solid components were released in the order of SO42− > AsO43− > Fe3+. The crystal tops were first dissolved, and the crystal surfaces were gradually smoothed/rounded until all edges and corners disappeared. The dissociations were restricted by the Fe-O(H) breakdown in the FeO6 octahedra and obstructed by the OH− and AsO4 tetrahedra outliers; the lowest concentration of the dissolved arsenic was 0.045 mg/L. Based on the dissolution experiment at 25°C and pH 2, the solubility products (Ksp) for the basic ferric sulfate-arsenate [Fe(SO4)0.27(AsO4)0.73 (OH)0.27·0.26H2O], which are equal to the ion activity products (logˍIAP) at equilibrium, were calculated to be -23.04 ± 0.01 with the resulting Gibbs free energies of formation (ΔGfo) of −914.06 ± 0.03 kJ/mol.

Towards the Understanding of Water-in-Salt Electrolytes: Individual Ion Activities and Liquid Junction Potentials in Highly Concentrated Aqueous Solutions

Highly concentrated electrolytes were recently proposed to improve the performances of aqueous electrochemical systems by delaying the water splitting and increasing the operating voltage for battery applications. While advances were made regarding their implementation in practical devices, debate exists regarding the physical origin for the delayed water reduction occurring at the electrode/electrolyte interface. Evidently, one difficulty resides in our lack of knowledge regarding ions activity arising from this novel class of electrolyte, it being necessary to estimate the Nernst potential of associated redox reactions such as Li⁺ intercalation or the hydrogen evolution reaction. In this work, we first measured the potential shift of electrodes selective to either Li⁺, H⁺ or Zn²⁺ ions from diluted to highly concentrated regimes in LiCl or LiTFSI solutions. Observing similar shifts for these different cations and environments, we establish that shifts in redox potentials from diluted to highly concentrated regime originates in large from an increase junction potential, it being dependent on the ions activity coefficients that increase with concentration. While our study shows that single ion activity coefficients, unlike mean ion activity coefficients, cannot be captured by any electrochemical means, we demonstrate that protons concentration increases by approximatively two orders of magnitude from 1 mol.kg^-1 to 15-20 mol.kg^-1 solutions. Combined with the increased activity coefficients, this increases the activity of protons and thus the pH of highly concentrated solutions which appears acidic.

Towards the Understanding of Water-in-Salt Electrolytes: Individual Ion Activities and Liquid Junction Potentials in Highly Concentrated Aqueous Solutions

Highly concentrated electrolytes were recently proposed to improve the performances of aqueous electrochemical systems by delaying the water splitting and increasing the operating voltage for battery applications. While advances were made regarding their implementation in practical devices, debate exists regarding the physical origin for the delayed water reduction occurring at the electrode/electrolyte interface. Evidently, one difficulty resides in our lack of knowledge regarding ions activity arising from this novel class of electrolyte, it being necessary to estimate the Nernst potential of associated redox reactions such as Li⁺ intercalation or the hydrogen evolution reaction. In this work, we first measured the potential shift of electrodes selective to either Li⁺, H⁺ or Zn²⁺ ions from diluted to highly concentrated regimes in LiCl or LiTFSI solutions. Observing similar shifts for these different cations and environments, we establish that shifts in redox potentials from diluted to highly concentrated regime originates in large from an increase junction potential, it being dependent on the ions activity coefficients that increase with concentration. While our study shows that single ion activity coefficients, unlike mean ion activity coefficients, cannot be captured by any electrochemical means, we demonstrate that protons concentration increases by approximatively two orders of magnitude from 1 mol.kg^-1 to 15-20 mol.kg^-1 solutions. Combined with the increased activity coefficients, this increases the activity of protons and thus the pH of highly concentrated solutions which appears acidic.

A New Approach to Establish Safe Levels of Available Metals in Soil With Respect to Potential Health Hazard of Human

Safe levels of extractable pollutant elements in soil have not been universally established. Prediction of metal solubility in polluted soils and the subsequent transfer of these metals from soil pore water to the human food supply via crops are required for effective risk assessment from polluted soils. Thus an attempt has been made to develop a novel approach to protect human health from exposure to toxic metals through assessing risk from metal polluted soils utilised for agriculture. In this study, we assess the relative efficacy of various forms of ‘free ion activity model’ (FIAM) for predicting the concentration of cadmium (Cd), lead (Pb), nickel (Ni), zinc (Zn) and copper (Cu) in spinach and wheat as example crops, thereby providing an assessment of risk to human health from consumption of these crops. Free metal ion activity in soil solution was estimated using the Windermere Humic Aqueous Model VII (WHAM-VII) and the Baker soil test. Approximately 91, 81, 75, 94 and 70% of the variability in Cd, Pb, Ni, Zn and Cu content, respectively, of spinach could be described by a FIAM using an estimate of the free ion activity of the metals provided by WHAM-VII. Higher prediction coefficients were obtained using EDTA, rather than DTPA, as the metal extractant in an integrated solubility-FIAM model. Out of three formulations, the FIAM, based on free ion activity of metals in soil pore water, determined from solution extracted with Rhizon samplers, was distinctly superior to the other formulations in predicting metal uptake by spinach and wheat. A safe level of extractable metal in soil was prescribed using a hazard quotient derived from predicted plant metal content and estimated dietary intake of wheat and spinach by a human population.

Antagonist Concepts of Polypyrrole Actuators: Bending Hybrid Actuator and Mirrored Trilayer Linear Actuator

Following the natural muscle antagonist actuation principle, different adaptations for “artificial muscles” are introduced in this work. Polypyrrole (PPy) films of different polymerization techniques (potentiostatic and galvanostatic) were analyzed and their established responses were combined in several ways, resulting in beneficial actuation modes. A consecutive “one-pot” electrosynthesis of two layers with the different deposition regimes resulted in an all-PPy bending hybrid actuator. While in most cases the mixed-ion activity of conductive polymers has been considered a problem or a drawback, here for the first time, the nearly equal expansions upon oxidation and reduction of carefully selected conditions further allowed to fabricate a “mirrored” trilayer laminate, which behaved as a linear actuator.