Highlights in Solute-Solvent InteractionsWolfgang Linert Most organic molecules retain their integrity when dissolved, and even though in such cases the effects exerted by solvents are, in the language of the coordination chemist, of the "outer sphere" kind, the choice of solvent can be critical to the successful outcome of an operation or preparation. Solubilities of reactants and products must be taken into account, and even if the organic principals in the reactions retain their integrity, many of the reagents are electrolytes, and their state of aggregation will affect their reactivity. In testifying to the importance of understanding solute-solvent interactions I draw attention to a large class of inorganic species for which the involvement in the chemical and physical properties by the solvent is even more deeply seated. It is comprised by the large body of metal atoms in low oxidation states for which solvent molecules intervene as reagents. At the same time, because the ions carry charges, the effects arising from outer sphere interactions are usually greater than they are for neutral molecules. To cite an example: when FeCb(s) is dissolved in water to form a dilute - say O. OlO- solution there is a complete reorganization of the coordination sphere of the cation. Whereas in the solid each cation is surrounded by six chloride ions, in the solution the dominant form is [Fe(H20)6]3+ followed by [Fe(H20)sCI]2+, [Fe(H20)4CI2]+, etc. in rapidly decreasing abundance. |
Contents
Ionic Solvation in Aqueous and Nonaqueous Solutions | 1 |
Spin Equilibrium in Solutions | 33 |
Thermochromism and Solvatochromism in Solution | 43 |
Recent Advances in the Description of the Structure of Water the Hydrophobic Effect and the LikeDissolvesLike Rule | 59 |
Thermodynamic Investigation of Phase Equilibria in Metal CarbonateWaterCarbon Dioxide Systems | 91 |
The SolventLike Nature of Silica Particles in Organic Solvents | 111 |
Prediction of Electrolyte Solubilities from Minimal Thermodynamic Information | 127 |
Preferential Solvation in Mixed Solvents X Completely Miscible Aqueous CoSolvent Binary Mixtures at 29815 K | 151 |
Phase Transitions and Critical Behaviour of Binary Liquid Mixtures | 177 |
Extraction of Unprotected Amino Acids by MixedLigand NickelII and CopperII Chelates | 197 |
Solvent Effects on IonPair Distribution and Dimerization of Tetraalkylammonium Salts | 203 |
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activity coefficients adsorbed anion apparent molar aqueous solution atoms behaviour binary calculated cavity formation chelates Chem Phys cm³ co-solvent complexes coordination correlation curves decreases density dimerization dxws dxww effect electrolyte enthalpy of formation entropy equations equilibrium EXAFS experimental data fluid function Gamsjäger H H-bonds heat capacity hydration hydration numbers hydrophobic Inorg Chem interactions ion pairs ionic strength Kirkwood-Buff integrals Königsberger ligand Linert liquid matrix measurements method mixtures molalities molecular NaCl nickel(II nonpolar octahedral Ohtaki H particles phase diagram Phe-Ala Phys Chem Pitzer equations Pitzer KS Pitzer model polarity preferential solvation parameters present model probe reaction shown in Fig silica simulations solubility constant Solution Chem solution chemistry solvation shell solvatochromic solvent solvent molecules species specific ion-interaction theory spin crossover structure studies Table Thermochromism thermodynamic thermodynamic properties thermonatrite Toftlund transition values Vmax volume-corrected preferential solvation water molecules whereas