Molecular simulation study on K^＋-Cl^- ion pair in geological fluids

This paper reports a classical molecular dynamics study of the potential of mean forces(PMFs),association constants,microstructures K^+-Cl^- ion pair in supercritical fluids.The constrained MD method is used to derive the PMFs of K^+-Cl^- ion pair from 673 to 1273 K in low-density water(0.10-0.60 g/cm).The PMF results show that the contact ion-pair(CIP) state is the one most energetically favored for a K^+-Cl^- ion pair.The association constants of the K^+-Cl^- ion pair are calculated from the PMFs,indicating that the K^+-Cl^- ion pair is thermodynamically stable.It gets more stable as T increases or water density decreases.The microstructures of the K^+-Cl^- ion pair in the CIP and solvent-shared ion-pair states are characterized in detail.Moreover,we explore the structures and stabilities of the KCl-Au(I)/Cu(I) complexes by using quantum mechanical calculations.The results reveal that these complexes can remain stable for T up to1273 K,which indicates that KCl may act as a ligand complexing ore-forming metals in hydrothermal fluids.

A molecular simulation study of Cs-Cl and Cs-F ion pairs in hydrothermal fluids

Magmatic-hydrothermal processes play an important role in the transport, enrichment, and mineralization of cesium. In this study, classical molecular dynamics simulations were performed to investigate the properties of Cs-Cl and Cs-F ion pairs in hydrothermal fluids. The association constants(log_(10)K_(A)(m)) under a wide range of temperature(i.e. 298–1273 K) and fluid density(i.e. 0.1–1.0 g/cm^(3)) were derived from the potential of mean force(PMF) curves. The results indicate that CsCl and Cs-F ion pairs have similar stabilities. This is different from other alkali metal cations(e.g., Li^(+), Na^(+), and K^(+)), which prefer binding with F over Cl. The stabilities of Cs-Cl and Cs-F ion pairs increase with increasing temperature(except for the fluid density ≤ 0.1 g/cm^(3)) or decreasing fluid density, which is similar to other alkali halide ion pairs. Comparisons among the stabilities of CsCl/F and other alkali halide ion pairs indicate that the Li–F ion pair has the highest stability in hydrothermal fluids.

Thermodynamics of Ion Pair of Magnesium Sulfate in Mixed Solvent

Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories of strong electrolyte behavior and to develop models of ion association in solution. Up to now, the ion pairs of magnesium sulfate in an aqueous solution have been widely investigated by using different experimental techniques, such as conductometry , cryoscopy potentiometry solubility and Raman spectrometry. However, to our knowledge, no measurement of the standard association constant of the ion pairs, [ MgSO4 ]^0 in a glucosewater mixed solvent is available.

Studies on Cyclodextrin Inclusion Complex by Fluorescence Anisotropy

An equation for determining the equilibrium association constant (KA) of cyclodextrin inclusion complex with fluorescence anisotropy is derived and used to determine KA of pyrene-B-cyclodextrin inclusion complex. The existing forms of cyclodextrin inclusion complex in solution, the interaction type of host with guest, and the possibility of application of B-cyclodextrin in the analysis of metal ions using naphthalene derivative as a ligand are discussed based on the equation derived along with the curve of fluorescence anisotropy versus cyclodextrin concentration of guest/cyclodextrin system.

Extraction Properties of Calix[4]arenes towards Sulphonated Dyes

Extraction of sulphonated dyes through supramolecular interaction with calix[4]arene derivatives is being presented here. The selectivity of calixarene derivatives namely piperidine derivative of calix[4]arene (calix-1), 1-methyl piperazine derivative of calix[4]arene (calix-2), and di-methyl amine derivative of calix[4]arene (calix-3) were evaluated initially against reactive red 2 (RR-2), acid black (AB), reactive blue 19 (B-19) and synthetic dye (D-2) by liquid-liquid extraction experiment. The results showed that the above three calixarenes possess excellent complexation abilities toward the selected dyes. The stoichiometric ratio for the calixarene derivatives and dyes was estimated through Job’s plot, whereas Hildebrand-Benesi equation was used to calculate formation constant (Ks) and molar absorptivity (Δε) of complexes. The binding association (Ka) and dissociation (Kd) constants were calculated by Scatchard plot additionally to further support the complexation data obtained from Hildebrand-Benesi equation. Conversely association constants from, both Hildebrand-Benesi equation and Scatchard plot i.e. Ks and Ka favor strong binding interaction between calix-1: D-2, calix-2: B-19, and calix-3: AB complexes. Thus present study adeptly supports the complexation of calixarene derivatives for sulfonated dyes.

Methyl Cholate and Resorcinarene New Carriers for the Recovery of Cr(Ⅲ) Ions by Supported Liquid Membranes (SLM)s

The technique of supported liquid membranes was used to achieve the facilitated transport of Cr(III) ions, using tow amphiphilic carriers, the methyl cholate and resorcinarene. For prepared SLMs, toluene as organic phase and film of polyvinylidene difluoride, as hydrophobic polymer support with 100 μm in thickness and 0.45 μm as the diameter of the pores. The macroscopic parameters (P and J0) on the transport of these ions were determined for different medium temperatures. For these different environments, the prepared SLMs were highly permeable and a clear evolution of these parameters was observed. The parameter J0 depended on the temperature according to the Arrhenius equation. The activation parameters, Ea, ΔH≠ and ΔS≠, for the transition state on the reaction of complex formation (ST) , were determined. To explain these results for this phenomenon, and achieve a better extraction of the substrate, a model based on the substrate complexation by the carrier and the diffusion of the formed complex (ST) was developed. The experimental results verify this model and determine the microscopic parameters (Kass and D*). These studies show that these parameters Kass and D* are specific to facilitated transport of Cr(III) ions by each of the carriers and they are changing significantly with temperature.

Photo-induced electron transfer between hypocrellins and nano-sized semiconductor CdS——EPR study on the kinetics of photosensitized reduction in HA-CdS and HB-CdS systems

Both HA-CdS and HB-CdS (Hys-CdS, Hys represents HA, HB) complex systems were established according to the dynamics of heterogeneous electron-transfer process ＜0. In these systems, the electron transferring from 1Hys* to conduction band of CdS is feasible. Determined from the fluorescence quenching, the apparent association constants (Kapp) between Hypocrellin A (HA), Hypocrellin B (HB) and CdS sol. were about 940 (mol/L)-1, 934 (mol/L)-1, respectively. Fluorescence lifetime measurements gave the rate constant for the electron transfer process from 1HA*, 1HB* into conduction band of CdS semiconductor as 5.16×109 s-1, 5.10×109 s-1, respectively. TEMPO (2,2,6,6-tetramethy-1-piperdinyloxy), a stable nitroxide radical, was used in the kinetic study of the reduction reaction taking place on the surface of a CdS colloidal semiconductor, kinetics equation of the reaction was determined with the electron paramagnetic resonance (EPR) method, and the reaction order of TEMPO is zero. When Hys were added, the rate of EPR increased greatly. By comparing rate constants, the Hys-CdS systems were revealed to be about 350 times more efficient than CdS sol. alone in the photoreduction of TEMPO under visi-ble light. It suggests that Hys can be used as efficient sensitizers of a colloidal semiconductor in the application of solar energy.