Quantitative description of the hydrophobic effect: the enthalpic contribution

A new method of experimental determination of the hydrophobic effect enthalpy is proposed. The method is based on regarding the hydration enthalpy as the sum of the nonspecific hydration enthalpy, specific hydration enthalpy, and the hydrophobic effect enthalpy. The hydrophobic effect enthalpies of noble and simple substance gases, alkanes, arenes, and normal aliphatic alcohols are determined. For the noble gases and alkanes, the hydrophobic effect enthalpy is found to be negative and independent of the size of molecule. For aromatic hydrocarbons, it is positive and grows up with the size of the hydrocarbon. The hydrophobic effect enthalpies of normal aliphatic alcohols are determined by assuming that the specific interaction enthalpies of alcohols in water and in methanol are equal. The hydrophobic effect enthalpy values for the aliphatic alcohols (-10.0 +/- 0.9 kJ.mol(-1)) were found to be close to the alkanes hydrophobic effect enthalpies (-10.7 +/- 1.5 kJ.mol(-1)).     

Evaluation of the contribution to hydration of nonelectrolytes from the hydrophobic effect

A new method was suggested for estimating the hydrophobic effect of contributions to the Gibbs energies and enthalpies of hydration of hydrocarbons, inorganic gases and rare gases. In accordance with this method the hydrophobic effect contribution to the Gibbs energy was evaluated from the difference between the hydration Gibbs energy of a solute and the non hydrophobic contribution. To estimate the latter value, the known dependence connecting the Gibbs energies of solvation of a solute in a number of aprotic solvents to the Hildebrand solubility parameter for these solvents was used. The non hydrophobic contribution to the Gibbs energy of hydration was calculated for various solutes from such dependences extended to water as solvent. The Hildebrand solubility parameter for water used in the calculation was corrected for the effect of association through hydrogen bonding. This correction was made by subtraction of the water self-association enthalpy from the enthalpy of vaporization of water. The evaluated Gibbs energies of the hydrophobic effect are positive for saturated hydrocarbons, inorganic gases and rare gases and linearly depend on the solute molecular refraction. The hydrophobic contribution to the hydration enthalpies of the solutes was calculated in the same manner as was made to calculate the hydrophobic contribution to Gibbs energies of hydration. Enthalpies of the hydrophobic effect for the solutes under study are negative.     

Hydrogen bonding of aliphatic and aromatic amines in aqueous solution: thermochemistry of solvation

Thermochemistry of hydration of the aliphatic and aromatic amines was studied. Enthalpies of solution at infinite dilution of amines in water were measured using the method of solution calorimetry. A procedure of taking into account the ionization and non-specific hydration of amines in aqueous media was carried out. A method for estimating the enthalpy of hydrogen bonding of amines in aqueous solutions was suggested on the basis of a comparative analysis of the solvation enthalpies of the solutes in water and methanol. The efficiency of this method is confirmed by evaluating the hydrophobic effect enthalpy.     

A method for calculating the Gibbs energies of hydrophobic effects and specific interactions of nonelectrolytes in aqueous solutions

The thermodynamic characteristics of hydrophobic hydration, the Gibbs energies of hydrophobic effect, were calculated. The method for calculations was based on the division of the Gibbs energy of hydration into contributions of nonspecific interactions, specific interactions between solutes and solvents (if they exist), and hydrophobic effect. In the absence of specific interactions between solutes and water, the Gibbs energy of hydrophobic effect depended linearly on the characteristic molecular volume of the solute for substances with different structures and properties. The universality of this dependence allows the suggestion to be made that it remains valid also in the presence of specific interactions. This allows the Gibbs energy of specific interactions in water to be determined for a wide range of compounds, in particular, for aliphatic alcohols.     

Excess volume of mixing and equation of state theories

Equation-of state theories of Flory and of Sanchez and Lacombe describe both enthalpy and volume of mixing of binary systems using single component properties and only one binary parameter X₁₂. We have evaluated this parameter from literature enthalpy data for numerous mixtures of two aromatic hydrocarbons, of alkanes with aromatic compounds, and of alkanes with carbonyl compounds. We have used this X₁₂ for calculation of excess volumes and compared the results with our previously measured experimental data. The agreement was fair for mixtures of two nonpolar components. Nevertheless, mixtures containing either cyclohexane or benzene displayed anomalies that could be traced to special packing of molecules in these compounds when pure. For mixtures of carbonyl compounds with alkanes, the theories predicted the qualitative trends correctly, but the quantitative agreement was rather poor. These results tend to support a model in which the enthalpy(cohesive energy) is inversely proportional to volume (as in the theories considered) only for dispersive interaction. When polar-polar interactions are involved, the dependence of excess volume on the excess enthalpy is much weaker.     

Heats of solution of gaseous hydrocarbons in water at 25°C

The heats of solution at 25°C for a number of hydrocarbon gases are reported as measured by a calorimetric method. There is excellent agreement between the standard enthalpy changes of solution measured calorimetrically and those derived from high precision temperature dependent solubility measurements. However the calorimetrically determined standard enthalpies of solution of a number of gases are greatly improved over values obtained from low precision temperature dependent solubility measurements. A method is presented to readily estimate the standard errors in the standard enthalpy change for any process derived from the temperature dependence of the equilibrium constant for the process. Comparison of the standard enthalpies and entropies of solution of hydrocarbon gases in water shows that the standard free energies of solution for all hydrocarbon gases investigated are dominated by unfavorable entropy contributions. A strong linear correlation between the standard entropy of solution and the number of hydrogens in the hydrocarbon molecule is found. This correlation suggests that the hydrocarbon hydrophobic effect is regulated by the number of allowable configurations of a water molecule in contact with each C–H group.     

Temperature and length scale dependence of tetraalkylammonium ion-amide interaction

We have studied the temperature and length scale dependence of the energetics of the pair interaction of well-established hydrophobic solutes tetraalkylammonium bromides with hydrophilic formamide (FA) and hydrophobic hexamethylphosphoric triamide (HMPT). Our results do indicate the anomalous length scale dependence of the tetraalkylammonium cation-amide interaction in water. As the cation size is increased, the unfavorable enthalpy of interaction is increased rather linearly until the maximum is reached, after which there appears to be a reversal of the trend. We believe that this phenomenon arises from the impossibility of water to maintain its H-bond network near large tetraalkylammonium cations that leads to the formation of a somewhat disordered solute hydration shell. The energetic cost for overlapping this shell with the amide hydration shell in water is noticeably smaller than that for tetraalkylammonium cations of a moderated size.     

Thermodynamics of solvation and solvophobic effect in formamide

Using semi-adiabatic calorimetry, we measured the enthalpies of solution for various low-polar compounds including alkanes, aromatic hydrocarbons and their halogenated derivatives in formamide at temperature of 298 K. For the same compounds, the values of limiting activity coefficients in formamide were determined using GC headspace analysis at 298 K, and Gibbs free energies of solution and solvation were calculated. Based on these data and the available literature values of the Gibbs free energy of solvation in formamide for a number of other low-polar solutes, a study of the solvophobic effect in this solvent is performed, and its resemblance to the hydrophobic effect in aqueous solutions is demonstrated. It is shown that the contribution of the solvophobic effect into the solvation Gibbs free energy in formamide is much higher than that in aliphatic alcohols, but lower than that in water. Like in water, the magnitude of this contribution for different solutes linearly increases with the solute molecular volume. Solvophobic effect also significantly affects the enthalpies of dissolution in formamide, causing them to be more negative in the case of alkanes and more positive in the case of arenes.     

The hydration of hydrophobic substances

A model of the hydration of hydrophobic substances in water is suggested. The models of fluctuation formation of empty cavities in water as a stage of hydration extensively used in the literature were shown to be at variance with experiment. The fundamental role played by the interphase boundary surface was emphasized. On this surface, the successive addition of water molecules with the formation of capsules around hydrophobic molecules occurred. The physical meaning of the Ostwald equation was revealed. This equation characterized the distribution of hydrophobic volatile substances between the gas and aqueous phases. The method of optical probes (hydrophobic aromatic molecules) was used to reveal the synergistic character of autocorrelation of dispersion interactions between water and hydrophobic substance molecules. This synergism was at variance with the Lennard-Jones potential. The synergism (superadditivity) of dispersion attraction forces, which strengthened their directional character, caused the self-organization and enhanced stability of hydration capsules with encapsulated hydrophobic molecules. Computer models were used to show that the spatially directional character of dispersion interactions necessary for the self-organization of hydrated aggregates could be simulated by the molecular mechanics method on the basis of orientational correlation of water molecules and hydrophobic substances in the starting system.     

The hydrophobic effect

This review is a brief discussion on the development of the understanding of hydrophobicity, or the hydrophobic effect. The hydrophobic effect is primarily discussed in terms of partitioning of hydrocarbons between a hydrophobic environment and water as well as solubility of hydrocarbons in water. Micellization of surfactants is only briefly reviewed.It is emphasized that (i) the cause of the hydrophobic effect, e.g. the low solubility of a hydrocarbon in water, is to be found in the high internal energy of water resulting in a high energy to create a cavity in order to accommodate the hydrophobe, (ii) the “structuring” of water molecules around a hydrophobic compound increases the solubility of the hydrophobe. The “structuring” of water molecules around hydrophobic compounds is discussed in terms of recent spectroscopic findings. It is also emphasized that (iii) the lowering of entropy due to a structuring process must be accompanied by an enthalpy that is of the same order of magnitude as the TΔS for the process. Hence, there is an entropy–enthalpy compensation leading to a low free energy change for the structuring process. The assumption of a rapid decay of the entropy with temperature provides an explanation of the enthalpy–entropy compensation so often found in aqueous systems. It is also emphasized (iv) that the free energy obtained from partitioning, or solubility limits, needs to be corrected for molecular size differences between the solute and the solvent. The Flory–Huggins expression is a good first approximation for obtaining this correction. If the effect of different molecular sizes is not corrected for, this leads to erroneous conclusions regarding the thermodynamics of the hydrophobic effect. Finally, (v) micellization and adsorption of surfactants, as well as protein unfolding, are briefly discussed in terms of the hydrophobic effect.     

Enthalpies of solvation of alkylated uracils in water,nonaqueous and mixed solvents

The enthalpies of solution of uracil and its alkylated derivatives in water, methanol, N,N-dimethylformamide (DMF) and water+DMF mixtures were measured at 25°C. The enthalpies of solvation were determined. The enthalpies of cavity formation, corresponding to the enthalpies of solvent-solvent interactions were calculated and the enthalpies of solute-solvent interactions were obtained. The presence of the alkyl groups was found to have different effects on the enthalpy of interaction depending on the position and size of the substitution. The effect of alkylation at the nonpolar side of the uracil ring was found to arise mostly from the enhancement of the van der Waals interactions. The alkyl substitutions at the polar side resulted also in the removal of the solvent molecules interacting specifically with the polar groups of uracil. The enthalpy of those specific interactions was determined and found to be stronger in methanol and DMF than in water. Enthalpies of solvation in the binary water+DMF solvent were found to depend in a nonlinear way on the solvent composition. The nonlinearities in the water-rich region were found to arise from the decay of the hydrophobic hydration of the solutes with the increasing DMF content. The substitution of two methyl groups caused the uracil molecule to bahave as a predominantly hydrophobic solute. The nonlinearities in the DMF-rich region were found only for those solutes which can form hydrogen bonds with DMF.     

True molar surface energy and alignment of surface molecules

By use of data for surface tension, for the first time a method is presented for calculating true molar surface properties of liquids: free energy, entropy, and enthalpy. These new data allow full comparison with other molar quantities, such as enthalpy and entropy of vaporization. All data are at the normal boiling point. There are differences in behavior between various classes of nonpolar compounds. Rare gases and tetrahydrides of Group 14 form a separate category. The results agree with the experimental findings that water and alcohol molecules are aligned with the -OH groups attached to the surface. The data indicate that hydrogen peroxide and 1,2-ethanediol also have one -OH group directed toward the surface and one directed out toward the vapor phase. Small straight-chain amines have some structure at the surface, but the larger ones behave like the corresponding alkanes. Very polar compounds, such as nitriles, nitro compounds, and aldehydes, have little or no increased degree of order of molecules at the surface. Except for hydrogen-bonded compounds, molecules at the surface have surroundings similar to those in the bulk liquid.     

Effect of carbon nanofiber functionalization on the adsorption properties of volatile organic compounds

The effect of the chemical activation, using HNO3, of a commercial carbon nanofiber (CNF) on its surface chemistry and adsorption properties is studied in this work. The adsorption of different alkanes (linear and cyclic), aromatic compounds and chlorohydrocarbons on both the parent and the oxidized CNF were compared. Temperature-programmed desorption results, in agreement with X-ray photoelectron spectroscopy experiments, reveal the existence of oxygen groups on the surface of the treated CNF. Capacity of adsorption was derived from the adsorption isotherms, whereas thermodynamic properties (enthalpy of adsorption, surface free energy characteristics) have been determined from chromatographic retention data. Both the capacity and the strength of adsorption decrease after the oxidant treatment of the carbon nanofibers, although in the case of chlorinated compounds the specific component of the surface energy shows an important increase. For n-alkanes and cyclic compounds, it was demonstrated that the presence of oxygen surface groups does not affect their interaction, the morphology of the surface being the key parameter. The oxidation of the nanofiber leads to steric limitations of the adsorption. In the adsorption of aromatic compounds, these limitations are compensated by the nucleophilic interactions between the aromatic ring and surface oxygenated groups, leading to similar performances of both materials. The absence of nucleophilic groups in the chlorinated compounds hinders their adsorption on the activated nanofibers.     

De-gassed water is a better cleaning agent

It is demonstrated that de-gassed water is more effective at dispersing hydrophobic "dirt", such as liquid hydrocarbons or oils. This effect appears to be due to the reduction of natural cavitation, which would otherwise oppose the dispersion of hydrophobic liquid droplets into water. De-gassing of the oil enhances this effect still further, and this has led to a proposal for a novel cleaning process, based on using a combination of a de-gassed (hydrophobic) solvent followed by rinsing in de-gassed water. This method might be useful as an effective, detergent-free cleaning process. Also reported are some initial studies which suggest that the effect of "inert" dissolved gases on the electrical conductivity of water may need to be reconsidered.     

Hydration of humic and fulvic acids studied by DSC

Qualitative and quantitative aspects of hydration of four humic acids (HA) and three fulvic acids (FA) originating from different sources were investigated. DSC experiments at subambient temperatures were carried out in order to monitor differences in ice behavior originating from freezable water surrounding humic molecules. It was found that kinetic effects play a significant role in hydration processes of both HA and FA. In fact, the hydration took part over 21?days which was detected as a progressive decrease in ice melting enthalpy. Simultaneously, the peak shapes and positions changed indicating structural changes in the physical structure of the humic substances. In case of FA, the dependency of melting enthalpy on water concentration showed a linear trend resembling a complete hydration previously observed for water-soluble hydrophilic polymers. In contrast, the melting enthalpy of some HA increased in a step-like way with increasing water content, suggesting preservation of original hydrophobic scaffold during the hydration. The differences between the rather young FA and the rather old HA lead to the conclusion that water can play a significant role in processes of humification. We assume that separation of hydrophobic and hydrophilic domains and thus increase in nanoscale heterogeneity represents an important physical contribution to the overall humification process. It was also demonstrated that the higher content of oxygen in humic molecules is not the only indicator of higher water holding capacity. Instead the porosity of humic matrix seems to contribute as additional parameter into these processes.     

A new angle on heat capacity changes in hydrophobic solvation

The differential solubility of polar and apolar groups in water is important for the self-assembly of globular proteins, lipid membranes, nucleic acids, and other specific biological structures through hydrophobic and hydrophilic effects. The increase in water's heat capacity upon hydration of apolar compounds is one signature of the hydrophobic effect and differentiates it from the hydration of polar compounds, which cause a decrease in heat capacity. Water structuring around apolar and polar groups is an important factor in their differential solubility and heat capacity effects. Here, it is shown that joint radial/angular distribution functions of water obtained from simulations reveal quite different hydration structures around polar and apolar groups: polar and apolar groups have a deficit or excess, respectively, of "low angle hydrogen bonds". Low angle hydrogen bonds have a larger energy fluctuation than high angle bonds, and analysis of these differences provides a physical reason for the opposite changes in heat capacity and new insight into water structure around solutes and the hydrophobic effect.     

Solvation and hydrophobic hydration of different types of alkylamines inN,N-dimethylformamide and water mixtures

Enthalpies of solution of twelve amines of different type have been determined at 25°C in mixtures of N,N-dimethylformamide and water over the whole composition range. The enthalpies of transfer from water to the mixtures deviate substantially from a linear dependence on the mole fraction of water. These deviations appear to contain additive contributions of the different alkyl groups. By application of a simple hydration model the enthalpic effect of hydrophobic hydration has been calculated for each amine. For alkylamines this is determined by the number and size of the alkyl groups present in the molecule. The contribution of each alkyl group is the same in primary, secondary and tertiary amines. Results for the different alkyl groups show a close relationship with values for alcohols obtained previously. Differences between alcohols and amines can be attributed to differences in the hydrophobic hydration of the parts of the solute molecules which are adjacent to the polar group. The influence of the polar group does not seem to extend beyond the second carbon atom.     

Potential of mean force of hydrophobic association: dependence on solute size

The potentials of mean force (PMFs) were determined for systems involving formation of nonpolar dimers composed of methane, ethane, propane, isobutane, and neopentane, respectively, in water, using the TIP3P water model, and in vacuo. A series of umbrella-sampling molecular dynamics simulations with the AMBER force field was carried out for each pair in either water or in vacuo. The PMFs were calculated by using the weighted histogram analysis method (WHAM). The shape of the PMFs for dimers of all five nonpolar molecules is characteristic of hydrophobic interactions with contact and solvent-separated minima and desolvation maxima. The positions of all these minima and maxima change with the size of the nonpolar molecule, that is, for larger molecules they shift toward larger distances. The PMF of the neopentane dimer is similar to those of other small nonpolar molecules studied in this work, and hence the neopentane dimer is too small to be treated as a nanoscale hydrophobic object. The solvent contribution to the PMF was also computed by subtracting the PMF determined in vacuo from the PMF in explicit solvent. The molecular surface area model correctly describes the solvent contribution to the PMF together with the changes of the height and positions of the desolvation barrier for all dimers investigated. The water molecules in the first solvation sphere of the dimer are more ordered compared to bulk water, with their dipole moments pointing away from the surface of the dimer. The average number of hydrogen bonds per water molecule in this first hydration shell is smaller compared to that in bulk water, which can be explained by coordination of water molecules to the hydrocarbon surface. In the second hydration shell, the average number of hydrogen bonds is greater compared to bulk water, which can be explained by increased ordering of water from the first hydration shell; the net effect is more efficient hydrogen bonding between the water molecules in the first and second hydration shells.     

Solvatochromic Linear Solvation Energy Relationships (LSER) for Solubility of Gases in Various Solvents by Target Factor Analysis

A linear solvation free energy relationship has been conducted to study the effects of solvent and solute properties on the free energy of solvation of inert gases and normal alkanes in different solvents. Factor analysis combined with target factor analysis was used to identify and quantify the factors controlling the variation of free energies of solvation, without the need to postulate any priori hypothetical method. Factor analysis of the solvation data revealed that there are two factors affecting the solubility of both types of gases in non‐polar as well as polar solvents. Target testing of the solvent parameters indicated that the Hildebrand solubility parameter of solvents is the major factor controlling the solubility of gases. Moreover, it was found that the coefficient of the Hildebrand solubility parameter in the linear solvation free energy equations has linear correlation with energy of vaporization and Lennard‐Jones force parameter of inert gases and number of carbon atoms and energy of vaporization of normal alkanes.