The structure,dynamics and solvation mechanisms of ions in water from long time molecular dynamics simulations: a case study of CaCl2 (aq) aqueous solutions

Systematic long time (5–20 ns) molecular dynamics (MD) simulations have been carried out to study the structural and dynamical properties of CaCl₂ aqueous solutions over a wide range of concentrations (≤9.26 m) in this study. Our simulations reveal totally different structural characteristics of those yielded from short time (≤1 ns) MD simulations [A.A. Chialvo and J.M. Simonson, J. Chem. Phys. 119, 8052 (2003); T. Megyes, I. Bako, S. Balint, T. Grosz, and T. Radnai, J. Mol. Liq. 129, 63 (2006)]. An apparent discontinuity was found at 4–5 m of CaCl₂ in various properties including ion–water coordination number and self-diffusion coefficient of ions, which were first noticed by Phutela and Pitzer in their thermodynamic modelling [R.C. Phutela and K.S. Pitzer, J. Sol. Chem. 12, 201 (1983)]. In this study, residence time was first taken into consideration in the study of Ca²⁺–Cl^? ion pairing, and it was found that contact ion pair and solvent-sharing ion pair start to form at the CaCl₂(aq) concentrations of about 4.5 and 4 m, respectively, which may be responsible for the apparent discontinuity. In addition, the residence time of water molecules around Ca²⁺ or Cl^? showed that the hydration structures of Ca²⁺ and Cl^? are flexible with short residence time (<1 ns). It needs to be pointed out that it takes much longer simulation time for the CaCl₂–H₂O system to reach equilibrium than what was assumed in previous studies.     

Aggregation phenomena and dynamics in II-I and III-I hydrated molten salts

Summary We present results from EXAFS and Raman scattering on aqueous solutions on II-I and III-I salts. As II-I salt the system investigated was the ZnCl₂ and its mixture with LiCl, CaCl₂ and SrCl₂. It was shown that ZnCl₂ evidences a tetrahedral arrangement around the Zn²⁺ ion whereas Li⁺, Ca⁺ and Sr²⁺ ions prefer an inner-shell water complexation. In particular it was shown that the tetrahedral units become less and less interacting when the ratio Cl⁻/Zn²⁺ is increasing. Such structural results are confirmed by the Raman probe that shows the vibrational bands becoming more and more localized for Cl⁻/Zn²⁺ values higher than 2. For what III-I salts are concerned we report results on SbCl₃/H₂O mixture. EXAFS evidenciates an Sb−Cl and Sb...Cl coordination very close to that of pure SbCl₃. The water molecule appears linked to the chlorine giving rise to a cross-link between SbCl₃ chains. Raman confirms such a result showing that the C_3v symmetry of SbCl₃ molecule is lowered in the presence of water and shows a new chlorine-water contribution plus a phononlike contribution in the very lowfrequency region. Paper presented at the workshop ?Highlights on Simple Liquids?, held in Turin at ISI on 1–3 May, 1989.     

Ions with strong symmetric H-bonds and their solvation in aqueous-ethanolic solutions of HCl

Ion-molecular interactions in the HCl-EtOH-H₂O system are studied by means of multiple frustrated total internal reflection IR spectroscopy over a wide range of concentrations of the components. It is demonstrated that, in the investigated solutions, the acid is fully bound into ions and uncharged complexes formed by strong symmetric or quasi-symmetric H-bonds. There is a competition between H₂O and EtOH molecules during the formation of the (H₅C₂(H)O…H…O(H)C₂H₅)⁺, (H₂O…H…OH₂)⁺, and (H₂O…H…O(H)C₂H₅)⁺ proton disolvates. In dilute solutions of HCl in 2: 1 and 1: 1 EtOH-H₂O mixtures, (H₂O…H…OH₂)⁺ proton dihydrates are mainly formed, whereas in concentrated HCl solutions, under conditions of a partial solvation of ions by solvent molecules, predominantly (H₂O…H…O(H)C₂H₅)⁺ mixed proton disolvates arise. In concentrated solutions of HCl in EtOH with low water content, the acid is partially bound into (H₅C₂(H)O…H⁺…Cl^?) uncharged complexes with the participation of the Cl^? anion.     

Solvation structure of magnesium,zinc, and alkaline earth metal ions in N,N‐dimethylformamide,N,N‐dimethylacetamide,and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

The solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N‐dimethylformamide (DMF) and N,N‐dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, respectively, in both DMF and DMA. The δ (O C N) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift Δν(= ν_bound − ν_free) becomes larger, when the ionic radius of the metal ion becomes smaller. The ν (N CH₃) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift Δν saturates for small ions, as well as the transition‐metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six‐coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent–solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift Δν in DMF–DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation of Sm3+–Eu3+ coactivating red-emitting phosphors and improvement of their luminescent properties by charge compensation

By charge compensating, a series of red-emitting phosphors Ca_0.54Sr_0.16Ca_0.54Sr_0.31Eu_0.08Sm_0.02(MoO₄)_0.6(WO₄)_0.4 were synthesized. Two approaches to charge compensation were used: (a) 2Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+M ⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ or K⁺; (b) Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+N ^?, where N⁺ is a monovalent anion like F^?, Cl^?, Br^?, or I^?. One red LED was made by combining the phosphor and 390–405 nm emitting LED chip under 20 mA forward-bias current, the color purity, chromaticity coordinates and the luminous intensity of which were 99.5%, x=0.66, y=0.33, 5600 mcd, respectively.     

Comparison of Inductively Coupled Plasma with Classical Analytical Techniques in the Analysis of Southern Oregon Lithia Water: Inclusion of a Local Resource in the Undergraduate Chemistry Curriculum

Abstract

Lithia water, a community resource of local historical significance, is described as a central theme in the undergraduate analytical chemistry sequence. A statistical comparison of the classical determination of major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (HCO₃ ^?, Cl^?) reinforces statistical and charge‐balance concepts covered in analytical chemistry. Subsequent determination of these major cations by inductively coupled plasma (ICP) enables students to statistically evaluate the presence of bias between instrumental and classical methods. The effect of easily ionized elements on ICP calibration sensitivity and linearity via the use of cesium as an ionization suppressor is reported.     

Calculation of the speed of sound in seawater from the known ion concentrations

It is shown that the method proposed earlier for calculating the speed of sound in seawater from the known ion concentrations, in a strict sense, can be applied for computing the sound speed in seas if, as a model of seawater, one uses a solution containing six ions or a solution containing four ions, namely, Na⁺, Mg²⁺, SO ₄ ^2? , and Cl^?, with the mole concentration of Na⁺ being replaced by the sum of mole concentrations of Na⁺ and K⁺ and the mole concentration of Mg²⁺ being replaced by the sum of mole concentrations of Mg²⁺ and Ca²⁺. An algorithm of calculation is proposed. It is demonstrated that, when the seawater is considered as a solution containing six ions, the computed value of the speed of sound does not depend on the choice of the specific ion whose concentration is determined from the condition of electric neutrality.     

Stability of aqueous silica nanoparticle dispersions

In this study, we present quantification methods for nanoparticle stability analysis using non-intrusive analytical techniques: attenuated total reflectance, Fourier transform infrared (ATR-FTIR) spectroscopy, ultraviolet–visible (UV–vis) spectrophotometer, zeta potential analyses, and dynamic light scattering (DLS). We use these techniques to study the stability of silica nanoparticle dispersions and the effects of pH, temperature, and electrolytes that would be encountered in oil field brines in a reservoir. Spectral analysis of the Si–O bond at wavenumber of 1110 cm⁻¹ with the ATR-FTIR indicates a structural change on the surface of silica particles as the dispersion pH changes, which agrees with zeta potential measurements. We define a critical salt concentration (CSC) for different salts, NaCl, CaCl₂, BaCl₂, and MgCl₂, above which the silica dispersion becomes unstable. Three distinct stages of aggregation occur in the presence of salt: clear dispersed, turbid, and separated phases. Divalent cations Mg²⁺, Ca²⁺, and Ba²⁺ are more effective in destabilizing silica nanoparticle dispersion than the monovalent cation Na⁺. The CSC for Na⁺ is about 100 times more than for Ca²⁺, Ba²⁺, and Mg²⁺. Among the divalent cations studied, Mg²⁺ is the most effective in destabilizing the silica particles. The CSC is independent of silica concentration, and lowers at high temperature.     

Conductance studies of NaCl, KCl, NaBr, NaI, NaBPh4, Bu4NI and NaClO4 in water + 2-methoxyethanol mixtures at 298.15 K

The electrical conductances of the solutions of sodium chloride (NaCl), potassium chloride (KCl), sodium bromide (NaBr), sodium iodide (NaI), sodium tetraphenylborate (NaBPh₄), tetrabutylammonium iodide (Bu₄NI) and sodium perchlorate (NaClO₄) in water (1) + 2-methoxyethanol (2) mixtures containing 0.01, 0.025, 0.05, 0.075, 0.10, 0.15 and 0.20 mol fractions of 2-methoxyethanol have been reported at 298.15 K. The conductance data have been analyzed by the Fuoss–Justice equation. The individual limiting ionic conductivities of Na⁺, K⁺, Bu₄N⁺, BPh₄⁻, I⁻, Cl⁻, and Br⁻ ions have been determined using the Fuoss–Hirsch assumption. The dependencies of the limiting molar conductances, Λ_o, and Walden products, Λ_oη, versus mixed solvent composition have been discussed.     

Electron Capture and Dissociative Excitation in Slow Collisions of Na+ and K+ Ions with Hydrogen and Nitrogen Molecules

Absolute cross sections of electron capture and dissociative excitation for the Na⁺-H₂, N₂ and K⁺-H₂, N₂ pairs are determined. The high intense hydrogen and nitrogen atomic lines HI (121.6 nm) NI (120.0 nm), have been observed. For the Na⁺-H₂ and K⁺-H₂ pairs the qualitative interpretation of experimental results in the framework of quasidiatomic approximation are carried out. This revised version was published online in July 2006 with corrections to the Cover Date.     

Improved luminescent properties of red-emitting Ca0.54Sr0.16Eu0.08Gd0.12(MoO4)0.2(WO4)0.8 phosphor for LED application by charge compensation

The red-emitting Ca_0.54Sr_0.16Eu_0.08Gd_0.12(MoO₄)_0.2(WO₄)_0.8 phosphor is improved in the emission charateristics by charge compensation, of which chromaticity coordinates (CIE) are x=0.66 and y=0.33. Three approaches to charge compensation are investigated, namely (a) 3Ca²⁺/Sr²⁺→2Eu³⁺/Gd³⁺+vacancy, (b) 2Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+M⁺(M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ employed as a charge compensator) and (c) Ca²⁺/Sr²⁺→Eu³⁺/Gd³⁺+N⁻ (N⁻ is a monovalent anion like F⁻, Cl⁻, Br⁻ and I⁻ employed as charge compensation ions). Through photoluminescent spectra analyzing the radiative and non-radiative relaxation mechanisms of luminescent system are obtained. Under 20 mA forward-bias current, one red-emitting LED is made by combining 390-405 nm-emitting LED chip and the phosphor. The red-emitting phosphor has broad prospects in LED application field.     

The Dependence of Benzo-15-Crown-5 Ether-Containing Oligo Paraphenylene Vinylene (CE-OPV) Emission Upon Complexation with Metal Ions in Solution

The effects of metal salts (NaCl, CaCl₂·2H₂O, EuCl₃·6H₂O and Eu(OAc)₃) on the steady state and time resolved fluorescence behaviour of poly(para phenylene vinylene) oligomers containing benzo-15-crown-5 ether units (CE-OPV) have been investigated. The presence of EuCl₃ causes a significant (8–9 fold) increase in the fluorescence emission intensity of the OPV segments, as compared to pure CE-OPV, in 99:1 methanol/chloroform solution and a small (9 nm) red shift in the emission maximum. The presence of Na⁺ or Ca²⁺ results in less marked increases in fluorescence intensity compared to Eu³⁺. In the presence of Eu³⁺ and Na⁺, the fluorescence intensity increases approximately linearly with metal ion concentration up to a metal ion/CE-OPV molar ratio of 10. The emission enhancement is not related to a simple 1:1 (CE-OPV:metal ion) complex formation process. In contrast, in acetonitrile, CE-OPV shows complex fluorescence quenching behaviour as a function of EuCl₃ concentration. This solvent dependence suggests that the emission changes with metal concentration are related to the formation of charge-transferred complexes. The marked changes in fluorescence quantum yield of the PPV backbone due to complexation with metal ions makes CE-OPV a sensitive fluorescent probe for metal ions, or may be exploited for improving the quantum yield of PPV-based devices.     

Photoluminescence of a soluble polypyrrole based on N-vinylpyrrole

Photoluminescence of a novel polypyrrole based on N-vinylpyrrole was systematically observed in organic solutions. The polymer, which has a unique molecular structure, exhibited good photoluminescence in organic solutions. The emission peak of the polymer exhibited one strong green emission band at around 510 nm in common organic solutions. The maximum fluorescence quantum yield of the polymer was found to be 0.16 in NMP solution with fluorescein as standard. At the same concentration, the photoluminescence intensity increased in the order of CHCl₃, THF, DMSO, CH₂Cl₂ and NMP. The photoluminescence spectrum had a slight red shift as the polarity of the solvents increased. The photoluminescence intensity also increased with the polarity of the solvent, except DMSO. This is because of its hygroscopicity in air and its viscosity. In THF solutions, the photoluminescence intensity increased until the concentration reached a certain weight percent (3.0×10⁻² wt.%) and then decreased with higher concentrations. This was most likely due to quenching in the aggregate phase. Furthermore, iron ion was a quencher in the DMSO solution. In a mixed solvent system of DMSO and water, water showed a typical quenching effect.     

Gap modes due to impurity pairs in ki

The pair modes due to Cl^?, Br^?, Na⁺W and Rb^v impurities in KI have been investigated using the Greens function technique. Group theory is used to put the final results as solutions of (2 × 2) determinants which could be tried by a hand calculator. Even a mass defect approximation reproduced the gap modes due to chlorine pairs, but in all cases a small change in the force constant, deduced from fitting single impurity gap modes, was used. The Raman active modes in all these cases were also computed.     

Ca2SiO4:Dy3+材料的制备及其发光特性

采用高温固相法制备了Ca₂SiO₄:Dy³⁺发光材料.在365nm紫外光激发下,测得Ca₂SiO₄:Dy³⁺材料的发射光谱为一多峰宽谱,主峰分别位于486nm,575nm和665nm处;监测575nm发射峰,测得材料的激发光谱为一多峰宽谱,主峰分别位于331nm,361nm,371nm,397nm,435nm,461nm和478nm处.研究了Dy³⁺掺杂浓度对Ca₂SiO₄:Dy³⁺材料发射光谱及发光强度的影响,结果显示,随Dy³⁺浓度的增大,黄、蓝发射峰强度比(Y/B)逐渐增大,利用Judd-Ofelt理论解释了其原因;随Dy³⁺浓度的增大,Ca₂SiO₄:Dy³⁺材料发光强度先增大,在Dy³⁺浓度为4 mol%时到达峰值,而后减小,根据Dexter理论其浓度猝灭机理为电偶极-电偶极相互作用.研究了电荷补偿剂Li⁺,Na⁺和K⁺对Ca₂SiO₄:Dy³⁺材料发射光谱的影响,结果显示,不同电荷补偿剂下,随电荷补偿剂掺杂浓度的增大,Ca₂SiO₄:Dy³⁺材料发射光谱强度的演化趋势相同,即Ca₂SiO₄:Dy³⁺材料发射峰强度先增大后减小,但不同电荷补偿剂下,材料发射峰强度最大处对应的补偿剂浓度不同,对应Li⁺,Na⁺和K⁺时,浓度分别为4mol%,4mol%和3mol%. 关键词： 白光LED 2SiO₄:Dy³⁺')" href="#">Ca₂SiO₄:Dy³⁺ 发光特性 电荷补偿     

X-ray structure refinement and ionic conductivity of Na6.69Ca3.355(SO4)6Cl0.77F0.63

The structure of Na_6.69Ca_3.355(SO₄)₆Cl_0.77F_0.63, isostructural with fluorapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed a space group P6₃/m with lattice parameters of a?=?9.477 (2) Å, c?=?6.865 (5) Å. Final refinement led to R _F?=?1.83 % and R _B?=?7.64 %. The location of Na⁺ ions in the M (2) sites surrounding the channels was related particularly to the high polarizability of the Ca²⁺. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at σ _500 °C?=?1.03?×?10^?5?S?cm^?1 and E_a?=?0.70 eV.     

Microscopic dynamics in water and ionic aqueous solutions: velocity cross-correlations

The microscopic momentum transfer between distinct particles in water and ionic aqueous solutions has been investigated by molecular dynamics simulation. The time correlation functions between the initial velocity of a central molecule and later velocities of molecules within different coordination shells were calculated for liquid water. Special attention was paid to the influence of the intermolecular hydrogen bonds on the exchange of momentum among water molecules and on the power spectra of the velocity autocorrelation functions. The velocity cross-correlations between ions in an aqueous NaCl solution also were calculated. It was observed that the difference between the results for the Na⁺ and Cl^? ions are associated mainly with the different sizes of the ions.     

Ion-exchange of monovalent and bivalent cations with NaA zeolite membranes : a molecular dynamics study

Molecular simulations using the method of molecular dynamics have been carried out to study the dynamics and energetics of ion exchanges between monovalent and bivalent cations in supercritical and subcritical (liquid) electrolyte solutions (here Li⁺, and Ca⁺⁺ in aqueous solutions of LiCl and CaCl₂) and an ion exchange membrane (NaA zeolite) using direct simulations of up to a nanosecond or more. NaA zeolites are widely used in many commercial ion-exchange processes including detergents. Results show that with appropriate driving forces, such ion exchange processes can be clearly witnessed and investigated using molecular simulations at these timescales, especially for supercritical solutions. An attempt is made to understand the phenomenon of ion exchange at the molecular level. Results have shown that the ion-exchange process is primarily energetically driven and entropic forces do not appear to be playing a significant role in the exchanges observed. For supercritical LiCl solutions, small differences were found between the energy of the Li⁺ inside and outside the membrane. In contrast, for Na⁺ there was a considerable energetic advantage in being outside the membrane, making the overall exchange process energetically favourable. In subcritical (liquid) LiCl solutions an exchange was found to be more favourable energetically than supercritical solutions. For Ca⁺⁺ similar trends were observed, except the differences in the energies were much larger (compared to the corresponding Li⁺ exchanges), making them more energetically efficient, as has also been observed experimentally. In addition to clarifying the molecular basis for these exchanges, simulations can also potentially be very useful to determine the behaviour (e.g. state dependence, etc.) of hydrodynamic parameters commonly used to characterize ion-exchange processes at a fundamental molecular level, and to determine if the hydrodynamic equations used for ion-exchange processes are applicable to nano-systems that can be studied using simulations.     

A theoretical prediction on the ground‐state complexes bound by metal ions to thymine base isomers

Stability orderings of 150 stable complexes formed by metal ions (Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺) and 13 stable thymine tautomers in both solvent and gas phases are obtained, and the optimal binding site for a metal ion in a specific thymine tautomer is identified. Results indicate that the complex with the canonical thymine tautomer (T1) is more stable than those with the rare ones, and the monodentate complex M–T1o4(o2) are their ground‐state form in the solvent phase. The ground‐state thymine complexes bound by Ca²⁺, Mg²⁺, or Zn²⁺ become bidentate M–T3o4lo2,n3, which is derived from a rare thymine tautomer T3o4l, whereas those bound by Na⁺ and K⁺ are still monodentate complexes M–T1o4(o2), however, in the gas phase. The differences in stability are discussed in detail from the binding strength of metal ions, relative energy of the corresponding thymine tautomers, and solution effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Comparison of the stability of thymine tautomers and the interaction of its tautomers with Na+, K+, Mg2+ and Ca2+ in gas and solvent phases

The present study compared the interactions among Na ⁺, K ⁺, Mg²⁺ and Ca²⁺, thymine and its tautomers in the gas and solvent phase, an interaction dependent upon the electronic construction of the tautomers. Three types of cation interaction with thymine and its tautomers were observed. In the first one, the metal cations interacted with a lone pair of nitrogen or oxygen of the tautomers. In the second type, there was an interaction among the cations, nitrogen and oxygen at the same time; the last one was that of cations with the electron density of thymine π-system, where the cations were perpendicular to the ring of thymine. The interaction of metals cation with tautomers was studied in the gas and solvent phases; a comparison was then made between interactions in two phases. The interaction energy for all complexes indicated the stability of complexes, an energy which was higher in Ca²⁺ and Mg²⁺ compared with Na⁺ and K⁺. Concerning K⁺ and Na⁺, the stability of all complexes of tautomers was greater than that of thymine complexes; however, the stability of certain Ca²⁺ and Mg²⁺ complexes was lower than the complexes of thymine.