Hydrophobic effect in aqueous solutions of nonelectrolytes. II. Cross-interactions of alkylureas

The heats of mixing of the aqueous solutions of monomethylurea, monoethylurea, 1,3-dimethylurea, 1,3-diethylurea were determined at 25°C. The excess enthalpies obtained are expressed in virial form, in terms of pair and triplet interaction coefficients. A method previously discussed for predicting the excess enthalpies and the interaction coefficients of ternary solutions has been applied to the alkylureas. The large deviations between the experimental and calculated values, led to the modification of that method, which better accounts for the marked mixed character of these substances.     

Nuclear magnetic resonance studies of aqueous solutions of alkylureas: Proton and carbon-13 chemical shifts

Aqueous solutions of methylated and ethylated derivatives of urea have been investigated by proton and carbon-13 magnetic resonance technique. The chemical shifts of water protons in solution of alkylureas, relative to that of pure water, are as a measure of the hydrogen-bonding reinforcing or weakening ability of these substances. The dependence of this effect on the concentration and on the temperature has also been studied. The results obtained indicate that different contrasting effects act in these solutions, among then the water structuring effect of the nonpolar surface of the alkylureas and the effect of the volume of the solute.¹³C chemical shifts of the carbonyl groups of the alkylureas give useful information about the interactions between water and the polar part of the ureas. Carbonyl-water interactions exist but are partially destroyed by increasing concentrations of the solute.     

Heat of dilution of monomethylurea in aqueous solutions at 25°C

The enthalpies of dilution of monomethylurea were determined by a flow microcalorimeter at 25°C. The data were combined with osmotic data to give the thermodynamic excess functions. The behavior of monomethylurea is compared to that of urea and other alkylureas, alkylamides, etc. in water. Enthalpy predominates at low concentrations, and entropy at higher concentrations. Hence monomethylurea falls within the group of substances whose behavior, according to Rowlinson, is “not peculiar in water”, for m<1. On the other hand, it must be considered a “peculiar aqueous” solute, for m>1. An analysis of the sign of the virial coefficients of the excess thermodynamic functions shows that the properties of MMU in solution are particular. These properties are briefly discussed on the basis of models proposed by Friedman and Krishnan for the aqueous solutions of predominantly hydrophobic solutes and by Frank and Franks for aqueous solutions of urea. Some preliminary data were presented at the International Conference on Chemical Thermodynamics held in Montpellier, 1975.     

Thermodynamic parameters of solvation of nonelectrolytes in aqueous solutions of amides of carboxylic acids

Interaction and reorganization contributions to solvation enthalpies of nonelectrolytes in aqueous solutions of amides of carboxylic acids with different degree of N-substitution and N-methylpyrrolidone are calculated. The data are discussed using structurally thermodynamic characteristics of water-amide systems obtained by us previously. It is found that the type of concentration dependence of the solvation enthalpy of nonelectrolytes in all solutions investigated is determined by the type of reorganization component. It is shown that the highest solvation exothermicity of nonelectrolytes in water is due to the lowest value of the reorganization contribution in spite of that nonelectrolytes interact weaker with water than with non aqueous components.     

Prediction of excess enthalpies for ternary aqueous solutions of nonelectrolytes

The excess enthalpiesH _xy ^E of ternary aqueous solutions of nonelectrolytes are used to test the possibility of making predictions for ternary solutions from the properties of the binary solutions only. Two methods are proposed: one is based on the empirical rule (h _xx ·h _yy )^1/2=h _xy . Another leads to the numerical prediction of the overallH _xy ^E . Both are successful for most of the pairs of solutes for whichH _x ^E ,H _y ^E >0.     

Temperature effect on the volume properties of a bisurea aqueous solutions

The densities of aqueous solutions of bisurea (2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione) were measured using a vibrating-tube densimeter at 288.15, 298.15, 308.15, and 318.15 K in the concentration range up to ∼3·10⁻³ moles of solute (1000 g of H₂O)⁻¹ with the error at most ±5· 10⁻⁶ g cm⁻³ (reproducibility up to 2·10⁻⁶ g cm⁻³). The limiting partial molar volume and expansibility of bisurea in water were calculated. The bicyclic molecules under study form in aqueous solution H-bonded hydrate complexes with rather high structure-packing density. These complexes are more subjected to the destroying effect of temperature than the corresponding urea complexes. The hydration of bisurea weakens with the temperature increase. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1929–1932, October, 2007.     

Thermodynamic activation parameters for viscous flow of dilute aqueous solutions of ethylenediamine,trimethylenediamine and N,N-dimethyltrimethylenediamine

The density and the viscosity data have been used to determine the thermodynamic activation parameters, free energies (ΔG ^?), enthalpies (ΔH ^?) and entropies (ΔS ^?), for viscous flow of the systems; water (W) + ethylenediamine (ED), W + trimethylenediamine (TMD) and W + N,N-dimethyltrimethylenediamine (DMTMD) in the temperature range of 303.15–323.15 K over the composition range of 0 ≤ X ₂ ≤ 0.45, where X ₂ is the mole fraction of diamines. On addition of diamines to water, ΔG ^?, ΔH ^? and ΔS ^? values increase sharply, pass through a maximum and then decline. The heights of maximum in the ΔG ^? versus X ₂ curve vary as, W + DMTMD > W + TMD > W + ED. For all systems, the excess properties, ΔG ^{? E} , ΔH ^{? E} and ΔS ^{? E} are positive. The observed increase in thermodynamic values may be due to combined effect of hydrophobic hydration of diamines and water–diamine interaction as a result of hydrophilic effect.     

Studies of hydrophobic bonding in aqueous alcohols: Enthalpy measurements and model calculations

The coefficients which measure the contribution of a pair of solute molecules to the excess enthalpy have been measured in water at 25°C for all pairs of alcohols which can be formed from the series methyl to n-butyl plus t-butyl as well as for ethanol with some of the higher alcohols and with the n-alkyl sulfonates through octyl. The methylene-group contribution to these coefficients is readily identifiable in suitable cases. These data and the corresponding free-energy and volume coefficients, where they are known, are analyzed in terms of amodel which specifies the core repulsion and solvation-layer overlap terms in the potential for the interaction of two solute molecules. The latter term has an adjustable parameter, the so-called Gurney free-energy parameter which is adjusted for each solute pair to fit the free-energy data. Its temperature and pressure derivatives are adjusted to fit the enthalpy and volume data, respectively. These parameters are compared with the corresponding thermodynamic coefficients of solvation as far as possible.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.A portion of the talk presented at the H. S. Frank Symposium has been published else-where. The discussion section at the end of this paper pertains mainly to that portion.     

The viscosity of aqueous solutions of alkali and tetraalkylammonium halides at 25°C

The viscosities of most alkali and tetraalkylammonium halides have been measured in water at 25°C. The relative viscosities can be fitted, up to 1M, with the relation _r =1+A c^1/2+B c+D ². TheA term depends on long-range coulombic forces, andB is a function of the size and hydration of the solute. When combined with partial-molal-volume data, the difference B –0.0025V° is mostly a measure of the solute-solvent interactions. IonicB are obtained if the tetraethylammonium ion is assumed to obey Einstein's law. TheD parameter depends on higher terms of the long-range coulombic forces, on higher terms of the hydrodynamic effect, and on structural solute-solute interactions. As such, it cannot be interpreted unambiguously.     

Influence of the size of fixed-rigidity spheres on the structural and energy characteristics of hydrophobic hydration

Monte Carlo simulations of molecular configurations of aqueous solutions of spherical particles with a special potential of solute—water interaction were carried out. The influence of the particle size on the properties of hydration shells was investigated. Two regimes of hydrophobic hydration with a crossover point at 0.4 nm were found. Hydration of smaller particles causes insignificant changes in the properties of water. Particles larger than 0.4 nm break the liquid water structure. Breaking effects are more pronounced in the first hydration shell of particles. Dewetting of hard sphere surfaces predicted by the LCW phenomenological theory has peculiarities in the case of hydration of fixed-rigidity spheres. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1777–1786, September, 2008.     

Structural contribution to the effect of hydrophobic hydration of noble gases

Within the concepts of structurally-thermodynamic characteristics of solvation and pseudo-chemical potential, the sample collection of the most authentic experimental data on solubility of gaseous He, Ne, Ar, Kr, Xe, and Rn in H₂O and D₂O is analysed at ≈0.1 MPa and T = 278–318 K. The conclusion is drawn that at deuteration of water molecules and also with increasing molar mass of noble gas, the relative contribution of effect of its hydrophobic hydration decreases. However in case of pass from lightweight noble gases (He, Ne, Ar) to heavy ones (Kr, Xe, Rn), structural transformations in their aqueous solutions become more expressed as a whole due to strengthening interaction between dissolved substance and solvent.     

Thermodynamic activation parameters for viscous flow of aqueous solutions of butylamines

The thermodynamic activation parameters, enthalpies, ΔH?^≠, free energies, ΔG ^≠, and entropies, ΔS?^≠, for viscous flow of the systems, water (W)?+?n-butylamine (NBA), W?+?sec-butylamine (SBA) and W?+?tert-butylamine (TBA), have been determined by using the density and the viscosity data. These properties and their excess values have been represented graphically against their composition. With respect to the composition, ΔG ^≠ show a typical behaviour for all the systems – a fast rise in the water-rich region with a maximum followed by the values that decline up to the pure state of amines. The ΔH?^≠ and ΔS?^≠ versus composition curves follow the similar trend. For all systems the excess properties, ΔG ^≠E, ΔH ^?≠E and ΔS?^≠E are characterized by sharp maxima in the water-rich region, which are thought to be mainly due to the hydrophobic hydration and the hydrophilic effect.     

A near-infrared study of the hydration of various ions and nonelectrolytes

The differential infrared absorption spectra of H₂O at 1200 nm and HOD/D₂O at 1450 nm have been recorded as function of temperature between 2 and 55°C. Following earlier investigations in the 1000 nm region,^(1,2) the data were interpreted on the basis of a hydrogen-bonding equilibrium invoking two states of the OH oscillators which are found to differ by a van't Hoff heat of formation of 2–3 kcal-mole^–1. The spectral changes induced by various non-electrolytes (1.0m) on the 1000 nm band have been recorded at 25°C for the following: tetrahydrofuran, tetrahydropyran, dioxane, dimethoxyethane, dimethyl sulfoxide, acetone, methyl acetate, propylene carbonate, dimethylformamide, dimethylacetamide, tetramethylurea, acetonitrile, and nitromethane. The specific influence of hydrocarbon chains on the near-IR absorption spectrum of water was further studied using a series of homologous sodiumn-alkyl carboxylates (formate to octanoate). The differential solvation spectra of three azoniaspiroalkane bromides have been obtained to compare the relative effects of cyclic and linear alkyl substituents. Finally, the study of ionic hydration effects has been extended to include the following electrolytes: NaPF₆, NaClO₄, NaBF₄, NaClO₃, NaNO₃, NaBrO₃, NaCN, NaSCN, Na₂SO₄, Na₂SO₃, Na₂CO₃, Na₂S₂O₃, MgCl₂, CaCl₂, BaCl₂, and SrCl₂. These data are discussed in terms of perturbations of the hydrogen-bonding equilibrium in water originating from one of the following: (1) direct OH... [polar group or anion] interactions, (2) structure-breaking effects due to weak OH... solute interactions, and (3) water-structure-promoting effects by alkyl groups.     

Thermodynamics of aqueous mixtures of nonelectrolytes. I. Excess volumes of water-n-alcohol mixtures at several temperatures

Excess volumes of binary mixtures of water with methanol, ethanol and 1-propanol were obtained from density measurements at 5 degree intervals from 15 to 35°C over the entire composition range. Excess thermal expansion coefficients, partial molar excess volumes, and expansibilities at 25°C were derived from the results. The significance of these values is discussed in relation to hypothesized structural changes in the mixtures.     

NMR chemical shifts of xenon in aqueous solutions of amphiphiles: A new probe of the hydrophobic environment

The chemical shift of elemental xenon in solution is sensitive to the environment. The shift arises from van der Waals interactions in most liquids, but an additional effect is present in aqueous media yielding a larger shift than expected. In water the shift is affected by the presence of low molecular weight amphiphiles, and its variation with composition can reveal the presence of hydrophobic hydration of the amphiphile. The results are similar to the conclusions drawn from other physical studies. Data are presented for aqueous solutions of methanol, ethanol, n-propanol, iso-propanol, tert-butanol, dimethylsulfoxide, p-dioxane, and acetonitrile.     

The hydrophobic interaction between macroscopic surfaces

The aim of this paper is to review our current level of knowledge of the interaction between hydrophobic surfaces immersed in water. The strong attractive forces observed between such surfaces have generally been referred to as “the hydrophobic interaction”. Although the precise origin of this force has not yet been determined, we will examine recent experimental studies and relate them to other phenomena like cavity formation and repulsive hydration forces.     

Dielectric spectroscopy on aqueous solutions of pyridine and its derivatives

The complex (dielectric) permittivity has been measured as a function of frequency between 1 MHz and 40 GHz for aqueous solutions of pyridine, 2- and 3-methylpyridine, as well as 2,4- and 2,6-dimethylpyridine at various temperatures and solute concentrations. Different relaxation spectral functions are used to analytically represent the data, in particular the Cole-Cole function. The solute contribution to the extrapolated static permittivity has been calculated to show that, in correspondence with other aqueous solutions of organic molecules and ions, the permittivity of the solvent seems to be enhanced with respect to the pure water value. Also in accordance with other aqueous systems it is found that the principal dielectric relaxation time for equimolar solutions of stereo isomers at the same temperature may significantly differ from one another. A further result is the finding of an unusually strong temperature dependence in the relaxation time of the 1 molar solution of 2,6-dimethylpyridine.     

Structral and thermodynamic characteristics and intermolecular interactions in aqueous solutions of diols

The structural and thermodynamic characteristics of aqueous solutions of ethanediol, 1,2-and 1,3-propanediols, and 1,2-and 1,4-butanediols were calculated over the whole range of the compositions of the mixtures. The specific and nonspecific components of the total energy of intermolecular interactions were determined. The boundaries of the concentration regions with different structural organizations of solutions were established, and the parameters of preferable solvation of the solution components were evaluated.     

Direct observation of hydrophobic interactions in aqueous solutions of organic compounds by supercooling and enthalpies of mixing

Supercooling temperatures and enthalpies of mixing with some solvents have been examined for two kinds of solutions subjected to different thermal treatments (solutions I and II) of tetrahydrofuran (THF), isopropyl alcohol (2-PrOH), and ethyleneglycol butylether (BE), and ethyleneglycol isobutylether (i-BE) in order to observe more directly the structural organization of water molecules around a nonpolar molecule in an aqueous solution. For THF and 2-PrOH solutions, supercooling temperatures of solution I were found to be 2–3 degrees higher than those of solution II, and differences H_I-H_II were found to be about 3 kJ mol^–1. It has been concluded that these results directly reflect the difference in the stability of hydrogen-bonded water networks in an aqueous solution.     

New data on the solubility of amorphous silica in organic compound-water solutions and a new model for the thermodynamic behavior of aqueous silica in aqueous complex solutions

Experimental solubilities of amorphous silica in several aqueous electrolyte solutions and in aqueous solutions of organic compounds, and theoretical considerations concerning cavity formation, electrostriction collapse, ion solvation, and long- and short-range interaction of the solvated ions with one another⁽¹⁾ permit the calculation of the partial excess free energies and the activity coefficients of aqueous silica. It is shown that, in the case of non-dissociated aqueous organic solutions, the variation of log m (SiO₂) with the reciprocal of the dielectric constant of the solution is described by a single linear equation independent of the nature of the organic compound. For aqueous electrolyte solutions, a specific linear relationship between log m (SiO₂) and the reciprocal of the dielectric constant occurs for each electrolyte. The success of the equation in reproducing the experimental solubilities of amorphous silica in aqueous solutions of electrolytes and organic compounds supports previous evidence indicating a polar charge distribution in the solvated SiO₂ molecule. Our data permit the calculation of the effective local charge of dissolved SiO₂ molecules and of the short-range interaction parameters between SiO₂ and various ions. The proposed equation of state can be used to calculate the affinity of reactions among SiO₂ minerals and complex aqueous solutions.