Aqueous Iodide Research Articles

Distinguishing Surface and Bulk Reactivity: Concentration-Dependent Kinetics of Iodide Oxidation by Ozone in Microdroplets.

Iodine oxidation reactions play an important role in environmental, biological, and industrial contexts. The multiphase reaction between aqueous iodide and ozone is of particular interest due to its prevalence in the marine atmosphere and unique reactivity at the air-water interface. Here, we explore the concentration dependence of the I- + O3 reaction in levitated microdroplets under both acidic and basic conditions. To interpret the experimental kinetics, molecular simulations are used to benchmark a kinetic model, which enables insight into the reactivity of the interface, the nanometer-scale subsurface region, and the bulk interior of the droplet. For all experiments, a kinetic description of gas- and liquid-phase diffusion is critical to interpreting the results. We find that the surface dominates the iodide oxidation kinetics under concentrated and acidic conditions, with the reactive uptake coefficient approaching an upper limit of 10-2 at pH 3. In contrast, reactions in the subsurface dominate under more dilute and alkaline conditions, with inhibition of the surface reaction at pH 12 and an uptake coefficient that is 10× smaller. The origin of a changing surface mechanism with pH is explored and compared to previous ozone-dependent measurements.

Structural Study of Aqueous Electrolyte Solution by MeV Liquid Electron Scattering.

The impact of ions on water has long been a subject of great interest, as it is closely tied to the hydration structure, dynamics, and properties of electrolyte solutions. Over centuries of investigation, the influence of ions on water's structure remains highly debated. Prevailing techniques, such as neutron and X-ray scattering, primarily focus on the microscopic structure of salt solutions at very high concentrations, mostly above 1 mol/L. In this study, we measured the structure of aqueous potassium iodide (KI) and potassium chloride (KCl) solutions using MeV liquid electron scattering (MeV-LES) across a concentration range of 0.10 to 0.75 mol/L. The obtained results provide detailed insights into the variations in ion-oxygen and oxygen-oxygen correlations as a function of concentration. The observed structural differences between KI and KCl solutions are in line with the structure maker/breaker theory, which suggests that iodide ions exert a more pronounced effect than chloride ions on disrupting the water shell. This work demonstrates the potency of MeV-LES for investigating the atomic structure in liquids, augmenting the modern analytical toolbox.

Spontaneous Production of I2 at the Surface of Aqueous Iodide Solutions.

Several groups have recently reported spontaneous production of atmospherically reactive species, including molecular iodine (I2) at the air-water interface of droplets. In this study, glancing angle laser-induced fluorescence spectroscopy was used to track the luminol fluorescence at the surface of sodium iodide (NaI) and sodium chloride (NaCl) solutions. Although luminol fluorescence is hardly quenched by halide anions, even up to fairly high concentrations, it is effectively quenched by I2. We observe luminol fluorescence quenching at the surface of NaI solutions but not at the surface of NaCl solutions, pointing to the formation of I2 at the surface of NaI solutions. This provides further support for the proposal that the strong electric field or the reduction solvation present at the air-water interface can initiate spontaneous iodide activation and other chemistry there. The spontaneous production of I2 at the surface of aqueous iodide solutions presents a previously unconsidered source of iodine in the atmosphere.

Dynamics of the charge transfer to solvent process in aqueous iodide

Charge-transfer-to-solvent states in aqueous halides are ideal systems for studying the electron-transfer dynamics to the solvent involving a complex interplay between electronic excitation and solvent polarization. Despite extensive experimental investigations, a full picture of the charge-transfer-to-solvent dynamics has remained elusive. Here, we visualise the intricate interplay between the dynamics of the electron and the solvent polarization occurring in this process. Through the combined use of ab initio molecular dynamics and machine learning methods, we investigate the structure, dynamics and free energy as the excited electron evolves through the charge-transfer-to-solvent process, which we characterize as a sequence of states denoted charge-transfer-to-solvent, contact-pair, solvent-separated, and hydrated electron states, depending on the distance between the iodine and the excited electron. Our assignment of the charge-transfer-to-solvent states is supported by the good agreement between calculated and measured vertical binding energies. Our results reveal the charge transfer process in terms of the underlying atomic processes and mechanisms.

Charge transfer reaction at gas-liquid interface of aqueous tetrabutylammonium iodide solution: influence of ions on dynamical response of solvent

Abstract Tetrabutylammonium iodide (TBAI) is known to create an electric double layer at the air-water interface. In the present study, we investigated the charge-transfer-to-solvent reaction from iodide ions to liquid water near the gas-liquid interface of an aqueous TBAI solution using extreme UV (EUV) time-resolved photoelectron spectroscopy. Use of EUV radiation ensured accurate measurements of electron kinetic energy distributions by minimizing spectral distortions caused by electron inelastic scattering in the liquid and the influence of the electron transmission efficiency through the gas-liquid interface. The spectra observed for photodetached electrons exhibited a rapid energy shift and a variation of the bandwidth in subpicoseconds, and the rates of these changes clearly depended on the TBAI concentration. The results indicate that the dynamical response of solvent water changes in the presence of a high density of ions.

Understanding the Anomalous Diffusion of Water in Aqueous Electrolytes Using Machine Learned Potentials.

The diffusivity of water in aqueous cesium iodide solutions is larger than that in neat liquid water and vice versa for sodium chloride solutions. Such peculiar ion-specific behavior, called anomalous diffusion, is not reproduced in typical force field based molecular dynamics (MD) simulations due to inadequate treatment of ion-water interactions. Herein, this hurdle is tackled by using machine learned atomic potentials (MLPs) trained on data from density functional theory calculations. MLP based atomistic MD simulations of aqueous salt solutions reproduce experimentally determined thermodynamic, structural, dynamical, and transport properties, including their varied trends in water diffusivities across salt concentration. This enables an examination of their intermolecular structure to unravel the microscopic underpinnings of the differences in their transport properties. While both ions in CsI solutions contribute to the faster diffusion of water molecules, the competition between the heavy retardation by Na ions and the slight acceleration by Cl ions in NaCl solutions reduces their water diffusivity.

Retention of Iodide by Chloride Green Rust and Magnetite.

Green rust (GR), a layered double hydroxide (LDH) containing Fe, and magnetite can be found in natural and engineered environments. The ability of chloride GR (GR-Cl) and magnetite to retain iodide as a function of various parameters was investigated. Sorption equilibrium is achieved within 1 day of contact time between iodide and preformed GR-Cl in suspension. pHm variations (7.5-8.5) have no significant influence, but the iodide sorption decreases with increasing ionic strength set by NaCl. Sorption isotherms of iodide suggest that the uptake operates via ionic exchange (IC), which is supported by geochemical modeling. The short-range binding environment of iodide associated with GR is comparable to that of hydrated aqueous iodide ions in solution and is not affected by pHm or ionic strength. This finding hints at an electrostatic interaction with the Fe octahedral sheet, consistent with weak binding of charge balancing anions within an LDH interlayer. The presence of sulfate anions in significant amounts inhibits the iodide uptake due to recrystallization to a different crystal structure. Finally, the transformation of iodide-bearing GR-Cl into magnetite and ferrous hydroxide resulted in a quantitative release of iodide into the aqueous phase, suggesting that neither transformation product has an affinity for this anionic species.

Correction to “Birth of the Hydrated Electron via Charge-Transfer-to-Solvent Excitation of Aqueous Iodide”

ADVERTISEMENT RETURN TO ARTICLES ASAPPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “Birth of the Hydrated Electron via Charge-Transfer-to-Solvent Excitation of Aqueous Iodide”Kevin Carter-Fenk*Kevin Carter-FenkMore by Kevin Carter-Fenkhttps://orcid.org/0000-0001-8302-4750, Britta A. JohnsonBritta A. JohnsonMore by Britta A. Johnson, John M. Herbert*John M. HerbertMore by John M. Herberthttps://orcid.org/0000-0002-1663-2278, Gregory K. SchenterGregory K. SchenterMore by Gregory K. Schenter, and Christopher J. Mundy*Christopher J. MundyMore by Christopher J. Mundyhttps://orcid.org/0000-0003-1378-5241Cite this: J. Phys. Chem. Lett. 2023, 14, XXX, 4150Publication Date (Web):April 27, 2023Publication History Received16 April 2023Published online27 April 2023https://doi.org/10.1021/acs.jpclett.3c01029© 2023 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views-Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (796 KB) Get e-Alerts Get e-Alerts

Silver ions immobilized on thiourea/formaldehyde resin for solid phase extraction of iodide ions from aqueous solution

Iodine has been found to have considerable effects on tropospheric photochemistry, which in turn affects climate by lowering ozone's radiative forcing and air quality by lowering extreme O3 concentrations in polluted areas. The majority of the iodine that naturally occurs in the water is in the form of aqueous iodide and iodate. To extract iodide from the aqueous solution, thiourea-formaldehyde resin (TF) was prepared by condensation polymerization and then loaded with Ag(I) ions (Ag-TF). TF resin was characterized by a specific surface area close to 111.3 m2 g−1, and nitrogen and sulphur content of 20.57 and 10.01 mmol g−1, respectively. After calculation of the adsorbed amount of Ag(I) ions, the prepared Ag-TF adsorbent was introduced for the solid phase extraction of iodide anions under various operational parameters of pH (e.g., 1.6 – 10.7), adsorbent dose (e.g., 0.5 – 5.0 g L−1), primary iodide concentrations (e.g., 0.075 – 3.96 mmol L−1), and residence time (e.g., 5 – 400 min), and sonication time (e.g., 5–45 min). The findings revealed that the adsorption of iodide onto as-produced TF adsorbent was matched with the Langmuir model with a prominent loading capacity of 1.26 mmol g−1, under an optimized pH value of 2.7. The study of uptake kinetics investigates the influence of the mode of agitation; comparing more specifically the performance of mechanical agitation with those obtained with ultrasonication (at frequencies of 37 and 80 kHz). The ultra-sonication treatment decreased interestingly the adsorption equilibrium time from 400 min to only 45 min. Overall, the present study illustrates the susceptibility of Ag-TF adsorbent as a promising material for the efficient elimination of I− anions from an aqueous medium.

Birth of the Hydrated Electron via Charge-Transfer-to-Solvent Excitation of Aqueous Iodide.

A primary means to generate hydrated electrons in laboratory experiments is excitation to the charge-transfer-to-solvent (CTTS) state of a solute such as I-(aq), but this initial step in the genesis of e-(aq) has never been simulated directly using ab initio molecular dynamics. We report the first such simulations, combining ground- and excited-state simulations of I-(aq) with a detailed analysis of fluctuations in the Coulomb potential experienced by the nascent solvated electron. What emerges is a two-step picture of the evolution of e-(aq) starting from the CTTS state: I-(aq) + hν → I-*(aq) → I•(aq) + e-(aq). Notably, the equilibrated ground state of e-(aq) evolves from I-*(aq) without any nonadiabatic transitions, simply as a result of solvent reorganization. The methodology used here should be applicable to other photochemical electron transfer processes in solution, an important class of problems directly relevant to photocatalysis and energy transfer.

Solvation thermodynamics of four amino acids in electrolytic solutions of sodium and potassium iodide salts at 298.15 K

The solubility and thermodynamics of solvation due to solute–solvent interactions of glycine, DL-alanine, DL-serine, and DL-valine were determined in this study. Mainly, the transfer of Gibbs free energies from aqueous to aqueous sodium and potassium iodide salt solutions was considered, which were calculated by direct experimental solubility data and via theoretical calculations. The equilibrium solubilities were measured at 298.15 K using simple “formol titration”. Various important physicochemical factors like enthalpy of solvation, molar volume, molar mass, molar density, etc., in aqueous electrolyte solutions were calculated at standard temperature. The thermodynamic parameters were explained to conclude about the virtual stability of the zwitterionic solutes in aqueous salt mixtures. The factors that are associated with solubility were also explained and correlated with physical and thermodynamic point of view.

Micro-CT in ophthalmology: ex vivo preparation and contrasting methods for detailed 3D-visualization of eye anatomy with special emphasis on critical point drying.

BackgroundMicro-computed tomography (micro-CT) provides detailed 3-dimensional (3D) visualization of anatomical structures and encourages morphological reinvestigation of organs with delicate features. The low radiodensity of soft tissues necessitates preceding sample preparation to conduct X-ray imaging with decent contrast between different tissues. In this study, we demonstrate the preparation with three radiopaque agents in combination with elimination of liquids by critical point drying (CPD) introduced for ocular samples.MethodsEnucleated porcine eyes were prepared with ethanolic iodine (EI), aqueous iodine-potassium iodide, or ethanolic phosphotungstic acid (EPTA). Micro-CT scans of the samples were conducted in a moist environment with an isotropic resolution of 9.2–12.5 µm voxel size. Subsequently, samples were chemically dehydrated and critical point (CP) dried to conduct a second scan in a dry environment with a resolution up to 4.7–5.4 µm in voxel size. The visualization effects were qualitatively and semi-quantitatively evaluated with regard to the generated contrast between different ocular tissues.ResultsAll three contrast agents accumulated well in most of the investigated ocular tissues and lead to an increased X-ray attenuation which allowed for differentiated visualization of ocular structures. Problematic agent penetration into the lens was obvious for iodine-potassium iodide and EPTA. Artificial damages of the lens and thickness reduction for the cornea and sclera due to CPD were noticed. The effects of the different contrasting treatments are described and compared with regard to the effects of CPD. Exclusively CP dried samples that were not treated with contrast agents could also be visualized excellently with a good distinction of different ocular structures from each other.ConclusionsAll ocular structures can be visualized by micro-CT. To contrast moist samples, the best results were achieved with iodine potassium iodide (IPI). CPD improved the scan quality in all cases. Even without pretreatment with contrasting agents, the CP dried samples showed a contrast similar to the IPI treated samples.

Nitrogen-doped porous carbon electrode for aqueous iodide redox supercapacitor

The incorporation of redox-active anions into aqueous electrolytes endows electrodes with enhanced specific energy density for supercapacitors. However, the congruent relationship between the redox chemistry of electrolytes and electrode surfaces is still not well understood. Herein, two-dimensional nitrogen-doped porous carbon nanosheets (denoted as NC-x with x being the carbonization temperature in Degree Celsius) are systematically synthesized by using general dual-crystals templating assisted strategy with pore structure and surface composition optimized. Employed as both positive and negative electrodes, the as-prepared NC-900 with a large specific surface area and ample graphitic N sites shows a high specific capacitance of 251 F g−1 with a voltage window of 1.6 V and energy density of 22.4 Wh kg−1 associated with 86.5% capacity retention after 30,000 cycles using aqueous iodide redox electrolyte. The experimental and theoretical analyses reveal the contributions of nitrogen configurations on the carbon scaffolds to accelerate the redox chemistry of iodides. The enhanced redox performance of the porous carbon nanosheets is linearly proportional to the graphitic N content, which is consistent with the large electron-donating area and the strong adsorption capacity towards iodine species at the graphitic N sites. This work shows a new design strategy of carbon electrodes for high-performance supercapacitors with the aqueous redox electrolytes.

Adsorption of Aqueous Iodide on Hexadecyl Pyridinium-Modified Bentonite Investigated Using an Iodine–Starch Complex

The sorption affinity of iodide on organo-bentonite, modified with hexadecyl pyridinium (HDPy), was investigated with the iodine–starch method coupled with UV/Vis absorption spectroscopy. The iodine–starch complex method was optimized in terms of the reaction time and sample compositions, based on the UV/Vis absorbance. The batch sorption experiment for iodide on organo-bentonites, modified using two different loading amounts of HDPy, was conducted to analyze the influence of equilibrium time, liquid-to-solid ratio, and temperature, on the iodide sorption affinity. The experimental results regarding the removal capacity were further employed to derive the distribution coefficients of iodide on the organo-bentonites. The novelty of this work lies in the first application of the iodine–starch method coupled with UV/Vis absorption spectroscopy for analyzing the sorption behavior of iodide on modified bentonites. It is expected that the iodide-starch method can be complementarily employed for future research, with respect to the quantification of iodide.

Long-Life Aqueous Zn-I2 Battery Enabled by a Low-Cost Multifunctional Zeolite Membrane Separator.

Aqueous zinc iodide (Zn-I2) batteries are promising large-scale energy-storage devices. However, the uncontrollable diffuse away/shuttle of soluble I3- leads to energy loss (low Coulombic efficiency, CE), and poor reversibility (self-discharge). Herein, we employ an ordered framework window within a zeolite molecular sieve to restrain I3- crossover and prepare zeolite molecular sieve particles into compact, large-scale, and flexible membranes at the engineering level. The as-prepared membrane can confine I3- within the catholyte region and restrain its irreversible escape, which is proved via space-resolution and electrochemical in situ time-resolution Raman technologies. As a result, overcharge/self-discharge and Zn corrosion are effectively controlled by zeolite separator. After replacing the typically used glass fiber separator to a zeolite membrane, the CE of Zn-I2 battery improves from 78.9 to 98.6% at 0.2 A/g. Besides, after aging at the fully charged state for 5.0 h, self-discharge is restrained and CE is enhanced from 44.0 to 85.65%. Moreover, the Zn-I2 cell maintains 91.0% capacity over 30,000 cycles at 4.0 A/g.

Sodium Iodide as a Contrast Agent for X-ray Micro-CT of a Wood Plastic Composite

The properties of wood plastic composites (WPCs) depend on their microstructure, particularly the level and geometry of wood reinforcement in the composite. We hypothesize that impregnating a WPC with a radiocontrast agent will increase the contrast between wood and plastic, allowing better visualization of its microstructure and numerical analysis of the geometry of its wood reinforcement. A commercial WPC was scanned using X-ray micro-CT, impregnated with aqueous sodium iodide, and then rescanned. CT data from both scans were visualized, and we analyzed the geometry of wood reinforcement and levels of wood, plastic, zinc borate (ZB), and voids in the WPC. ZB occurred mainly as discrete particles between wood flakes, and interfacial voids formed a network of cracks within the WPC. Sodium iodide labeling made it possible to clearly visualize wood and plastic in the WPC and quantify levels of different phases and the geometry of wood particles. However, sodium iodide was not an ideal contrast agent because it swelled wood particles, closed interfacial voids, and partially dissolved ZB particles. We suggest methods of overcoming these limitations and conclude that advances in labeling are necessary to improve our understanding of the relationship between the microstructure of WPCs and their properties.

Elaborating the Iodine/Polyiodide Equilibrium Effects in Nanoporous Carbon-based Battery Electrode via Extreme Mass Asymmetry in Hybrid Cells.

This article discusses the conversion of electrodeposited iodine to polyiodides within the nanopores of carbon electrodes that affect the performance of iodide electrolyte‐based electrochemical cells. Here, carbon electrodes have been polarized in aqueous sodium iodide electrolyte to store charge in the form of solid iodine via highly reversible reaction (2I−⇌I2+2e−). The stored iodine within the pores interacts with free iodide ions present in the bulk electrolyte via comproportionation reactions leading to polyiodide (I3 − and I5 −) formations. By tuning the mass asymmetry of carbon electrodes in hybrid cells and using the in‐situ Raman spectroscopy on positive battery electrode, we show the influence of iodine/polyiodides equilibrium shifts on the self‐discharge and voltage rebounds during open circuit conditions. This study provides insights into the charging mechanisms of carbon electrodes for iodine‐based hybrid supercapacitors and battery systems.

Sensitivity of Iodine-Mediated Stratospheric Ozone Loss Chemistry to Future Chemistry-Climate Scenarios

As the chemical and physical state of the stratosphere evolves, so too will the rates of important ozone-destroying reactions. In this work, we evaluate the chemistry-climate sensitivity of reactions of stratospheric iodine, reporting the iodine alpha factor (the efficiency of ozone loss mediated by a single iodine atom relative to the ozone loss mediated by a single chlorine atom) and the iodine eta factor (the efficiency of ozone loss mediated by a single iodine atom relative to the ozone loss mediated by a single chlorine atom in a benchmark chemistry-climate state) as a function of future greenhouse gas emissions scenario. We find that iodine-mediated ozone loss is much less sensitive to future changes in the state of the stratosphere than chlorine- and bromine-mediated reactions. Additionally, we demonstrate that the inclusion of the heterogeneous reaction of ozone with aqueous iodide in stratospheric aerosol produces substantial enhancements in the iodine alpha and eta factors relative to evaluations that consider gas-phase iodine reactions only. We conclude that the share of halogen-induced ozone loss due to reactions of iodine will likely be greater in the future stratosphere than it is today.

Spatial and Temporal Variability of Iodine in Aerosol

AbstractIn this work, we describe the compilation and homogenization of an extensive data set of aerosol iodine field observations in the period between 1963 and 2018 and we discuss its spatial and temporal dependences by comparison with CAM‐Chem model simulations. A close to linear relationship between soluble and total iodine in aerosol is found (∼80% aerosol iodine is soluble), which enables converting a large subset of measurements of soluble iodine into total iodine. The resulting data set shows a distinct latitudinal dependence, with an enhancement toward the Northern Hemisphere (NH) tropics and lower values toward the poles. This behavior, which has been predicted by atmospheric models to depend on the global distribution of the main oceanic iodine source (which in turn depends on the reaction of ozone with aqueous iodide on the sea water‐air interface, generating gas‐phase I2 and HOI), is confirmed here by field observations for the first time. Longitudinally, there is some indication of a wave‐one profile in the tropics, which peaks in the Atlantic and shows a minimum in the Pacific. New data from Antarctica show that the south polar seasonal variation of iodine in aerosol mirrors that observed previously in the Arctic, with two equinoctial maxima and the dominant maximum occurring in spring. While no clear seasonal variability is observed in NH middle latitudes, there is an indication of different seasonal cycles in the NH tropical Atlantic and Pacific. Long‐term trends cannot be unambiguously established as a result of inhomogeneous time and spatial coverage and analytical methods.

Thermodynamics of Solute–Solvent Interactions and Solubility of Some Amino Acids in Aqueous Sodium Iodide Solutions at T = 298.15 K

Thermodynamics of Solute–Solvent Interactions and Solubility of Some Amino Acids in Aqueous Sodium Iodide Solutions at T = 298.15 K