Monte Carlo simulations of the hydrophobic effect in aqueous electrolyte solutions

The hydrophobic interaction between two methane molecules in salt-free and high salt-containing aqueous solutions and the structure in such solutions have been investigated using an atomistic model solved by Monte Carlo simulations. Monovalent salt representing NaCl and divalent salt with the same nonelectrostatic properties as the monovalent salt have been used to examine the influence of the valence of the salt species. In salt-free solution the effective interaction between the two methane molecules displayed a global minimum at close contact of the two methane molecules and a solvent-separated secondary minimum. In 3 and 5 M monovalent salt solution the potential of mean force became slightly more attractive, and in a 3 M divalent salt solution the attraction became considerably stronger. The structure of the aqueous solutions was determined by radial distribution functions and angular probability functions. The distortion of the native water structure increased with ion valence. The increase of the hydrophobic attraction was associated with (i) a breakdown of the tetrahedral structure formed by neighboring water molecules and of the hydrogen bonds between them and (i) the concomitant increase of the solution density.     

Short-range potential functions in computer simulations of water and aqueous solutions

A review and comparative analyses of methods for restricting the range of molecular interactions within the concept of atom-atom potentials are presented. Emphasis is placed on the problem of calculating the electrostatic energy in models with periodic boundary conditions. Numerous calculations of the thermodynamic and structural characteristics of water using parallel Monte Carlo computations have shown that the use of functional forms simulating the electric potentials of “screened charges” provides very good results.     

Acceleration of convergence in Monte Carlo simulations of aqueous solutions using the metropolis algorithm. Hydrophobic hydration of methane

Convergence problems encountered in the computer simulations of aqueous solutions are discussed. Solute–solvent radial distribution functions are shown to converge very poorly when the standard Metropolis Monte Carlo procedure is applied. To overcome this difficulty, several modifications are made in the Metropolis method. Optimum maximum step sizes are determined for simulations of liquid water. A scheme is employed for preferential sampling of both the solvent and the solute molecules. To test these modifications, a simulation is carried out for pure liquid water, treating a single water molecule as a “solute.” The convergence of the radial distribution functions is found to be accelerated significantly. A further test is made by simulating an aqueous solution of methane, consisting of one methane molecule (using the EPEN /2 potential for methane–water interactions) and 124 water molecules (using the MCY potential for water–water interactions). Again, the convergence of solute–solvent radial distribution functions is found to be accelerated. The computation of partial molar thermodynamic quantities, however, still suffers from convergence difficulties. This problem is discussed in detail. The EPEN /2 potential is found to yield structural and thermodynamic features of hydrophobic hydration that are consistent with available experimental and theoretical results for aqueous solutions of methane.     

Estimated ionicB-coefficients from NMR measurements in aqueous electrolyte solutions

¹⁷O-NMR spin-lattice relaxation timesT ₁ of D₂O molecules were measured at 5–85°C in D₂O solutions of alkali metal halides (LiClCsCl, KBr, and KI), DCl, KOD, Ph₄PCl, NaPh₄B, and tetraalkylammonium bromides (Me₄NBrAm₄NBr) in the concentration range 0.1–1.4 mol-kg^–1 TheB-coefficients of the electrolytes obtained from the concentration dependence of relaxation ratesR ₁=1/T₁ were divided into the ionicB-coefficients by three methods: (i) the assumption ofB (K⁺)=B(Cl^–), (ii) the assumption ofB(Ph₄P⁺)=B(Ph₄B^–), and (iii) the use ofB(Br^–) obtained from a series ofB(R₄NBr). It was found that Methods (ii) and (iii) resulted in an abnormal temperature dependence of theB-coefficients of alkali metal ions and a negative values of rotational correlation times _c at lower temperatures for hydroxide and halide ions. These results suggest that the methods based on the van der Waals volume are not adequate for the ionic separation of NMRB-coefficients. From the analysis using the assumption ofB(K⁺)=B(Cl^–), it was found that D₃O⁺, OD^–, and Me₄N⁺ ions are the intermediates between structure makers and breakers, and that the hydrophobicity of phenyl groups is weaker than that of alkyl groups due to the interactions between water molecules and -electrons in phenyl groups.     

Glasslike behavior in aqueous electrolyte solutions

When salts are added to water, generally the viscosity increases, suggesting that the ions increase the strength of the water's hydrogen-bond network. However, infrared pump-probe measurements on electrolyte solutions have found that ions have no influence on the rotational dynamics of water molecules, implying no enhancement or breakdown of the hydrogen-bond network. Here, we report optical Kerr effect and dielectric relaxation spectroscopic measurements, which have enabled us to separate the effects of rotational and transitional motions of the water molecules. These data show that electrolyte solutions behave like a supercooled liquid approaching a glass transition in which rotational and translational molecular motions are decoupled. It is now possible to understand previously conflicting viscosity data, nuclear magnetic resonance relaxation, and ultrafast infrared spectroscopy in a single unified picture.     

Investigation of cesium uptake from aqueous solutions using new titanium phosphates ion-exchangers

The uptake of cesium from aqueous solutions (pH 5) using titanium phosphates was investigated in the absence and presence of background electrolyte (0.1 M NaNO₃) using a batch technique. The determination of cesium was performed by gamma spectroscopy using ¹³⁷Cs as tracer. The obtained sorption isotherms could be satisfactorily reproduced by a Langmuir sorption equation. The maximum uptake capacity values (q _max) calculated fitting the experimental data by this equation were 167 and 118 mg/g for solutions of initial pH 5 in the absence and presence of background electrolyte. Kinetics data obtained at 293, 308 and 323 K could satisfactorily reproduced by the pseudo-second order equation. It was demonstrated that the new synthesized materials can remove considerable amounts of cesium from aqueous solutions and ion exchange is considered to be the principal mechanism for cesium removal. Toxicity characteristic leaching procedure and desorption tests provided data about the application of the sorbents in environmental remediation.     

Thermal motion from monte carlo simulations of aqueous ionic solutions

The statistical pattern recognition procedure of Marchese and Beveridge for the analysis of Monte Carlo simulations of aqueous ionic solutions [J. Am. Chem. Soc. 106 , 3713 (1984)] has been extended to include average hydrogen positions as well as oxygen positions. In addition, thermal ellipsoids have been calculated for each atom and displayed graphically. Application of this procedure to the analysis of a dilute aqueous solution of Zn⁺⁺ reveals an octahedral arrangement of water molecules within the ion's first hydration shell. The thermal ellipsoids show that most of the water motion is manifest in the hydrogen atoms.     

Enthalpy changes of salting processes of hen-egg white lysozyme in various electrolyte solutions

The enthalpy changes of salting process of hen-egg white lysozyme in buffer acetate solutions (pH=4.25) as a function of concentration of following electrolytes: LiCl, KCl, K₂SO₄, Li₂ SO₄ and (NH₄)₂SO₄ are determined. Obtained data according to McMillan and Mayer’s approach, has been analyzed in the terms of the enthalpic pairwise interaction coefficients: lysozyme – lysozyme h_xx, and lysozyme – salt h_xy. The ability of cations to precipitate lysozyme solution in relation to the concentration of cations can be seen from the series as follows: Li⁺> Na⁺>K⁺>NH₄+⁺     

Design simulations for a biogas purification process using aqueous amine solutions

Using the simulation program CHEMCAD, performance characteristics, design optimization, and costs of an absorption/stripping system used to purify 100 kg h^?1 of biogas in a biogas power plant were investigated. Potential absorbents used in the chemical absorption process were the following aqueous solutions: pure diglycolamine, diglycolamine/piperazine, and diglycolamine/methyldiethanolamine/piperazine. Mixtures for agricultural biogas purification to below 1 vol. % of CO₂ and 4 × 10^?4 mass % of H₂S were determined via a simulation in the above mentioned program. The chosen mixtures were then entered into an absorption/desorption system and simulations for each unit were provided by CHEMCAD. From the simulation results, the design parameters were calculated and entered into each unit??s ??cost estimation?? section in the aforementioned program to estimate the purchase costs of the apparatuses. Taking into account the installation, maintenance, as well as other additional costs, the actual machine purchase costs were multiplied by the Lang factor. Costs of additional streams were also calculated by multiplying the ten-year utility losses by their respective cost factors. From these calculations, the absorbent mixture, allowing biogas production at the lowest estimated costs for ten years, was found.