Effect of coexistent hydrocarbon phase on the volume behavior of adsorbed film and micelle of dodecyltrimethylammonium chloride

Interfacial tension () between aqueous dodecyltrimethylammonium chloride (DTAC) solution and benzene was measured as a function of pressure (p) and concentration. The/p was observed to change discontinuously at the critical micelle concentration; this indicates that the micelle formation of DTAC in the aqueous solution coexisting with benzene can be treated like the appearance of a macroscopic phase. It was shown by drawing the vs.A curves that hydrocarbon, such as benzene, cyclohexane, and hexane, make the adsorbed film of DTAC expand. The volume behavior of the micelle with benzene molecules solubilized was found to bear a strong resemblance to that of the adsorbed film at the water/benzene interface. The difference in the molar volume value of adsorbed DTAC among the coexistent hydrocarbon phases was attributed to the difference in the contribution of the hydrocarbon molecules to the interfacial excess volume; the number of the solubilized hydrocarbon molecules was evaluated to be one or two a micelle.     

Thermodynamics of the Solubility of Water in 1-Hexanol, 1-Octanol, 1-Decanol, and Cyclohexanol

Summary. The solubility of water in 1-hexanol, 1-octanol, 1-decanol, and cyclohexanol was determined as a function of water activity by the isopiestic method at 298.2K. The solubility of water in the alcohol was expressed by a Setchenov type of equation and the correlation coefficients were related to the virial coefficients of the McMillan-Mayer theory of solution. From the solubility data both the activities and the osmotic coefficients of the alcohols were calculated. The Henrys law constants for the solubility of water in the alcohols are given. They depend linearly on the Gibbs energy of hydration. The excess Gibbs energy of mixing of water and alcohols is positive as a consequence of the strong intermolecular interactions of the two pure components of the mixture.     

Effects of Salts of Varying Nature on the Energy Stability of the Structure of Aqueous Solutions

For cyclopentane used as a model hydrocarbon, solubility in water and aqueous solutions of various salts (chlorides, bromides, iodides, rhodanides, alkali metal acetates and sulfates, and calcium and zinc chlorides) at 20±1°C has been determined. Variations of the increment of the methylene group ( ) induced by salt additions to water, are calculated. When the salt is added to the solution, the increment increases drastically irrespective of the nature of the ions, thus stabilizing the structure of the solution. The increase, however, depends significantly on the nature of the salt, which is explained by different degrees of structuring of the aqueous solution caused by the ions of the salts.     

The Energy of Interaction between Water Monolayer and Carbon Surface and the Determination of H-Bond Energy from the Isotherms of Water Desorption by Organic Molecules into an Aqueous Solution

It is proven that, when passing from a liquid into an adsorption phase on a carbon surface, the maximal number of H-bonds between water molecules decreases from four to three because of the screening of one unpaired electron of the oxygen atom of an adsorbed water molecule by aromatic rings of the carbon surface. An energy gain equal to the energy of one H-bond arises upon water desorption by organic molecules adsorbed from an aqueous solution. The ratio between the number of H-bonds of a group of water molecules, which is displaced into a solution by one organic molecule, in the solution and in the adsorption phase is independent of the number of molecules in this group and is, on the average, equal to 2.038 for all possible structures of H-bonds in both phases. The allowance for this ratio in the isotherm of water desorption into a solution and the introduction of a coefficient, which depends on the relative water content ( ) in the adsorption phase, in the form of into the equation of the desorption isotherm make it possible to determine the balance of the change in the Gibbs energy at the desorption equilibrium and the standard Gibbs energy = –1.76 kJ/mol of water desorption into a solution from a carbon surface. This value determined by an independent method is = –1.79 kJ/mol; i.e., both values are close to each other. The RTlnf energy of the additional H-bond, which is formed between water molecules upon passing from the adsorption phase into the solution, is found by the extrapolation of the isotherms of water desorption by molecules of several benzene derivatives. This energy ranges from 9.13 to 9.24 kJ/mol, thus corresponding to the energy of one H-bond, as measured by IR spectroscopy and NMR.     

Effects of Cyclodextrins on Dodecane Biodegradation

Bioremediation of non-chlorinated hydrocarbon-polluted soils is mainly affectedby low bioavailability, due to hydrophobicity of these xenobiotics. In fact, severalmicroorganisms can use hydrocarbons as energy and carbon sources, but theirdegradative activity takes place into the aqueous phase of the soil, where just tracesof hydrocarbons are found because of their low water solubility. So, natural attenuationusually occurs in hydrocarbon-polluted soils, but this process is very slow. It has alreadybeen demonstrated that cyclodextrins increase hydrocarbon solubility and bioavailabilityand accelerate their biodegradation. In this work it was investigated if their efficacy onbiodegradation of a model hydrocarbon (dodecane) is affected by the kind (,-, - and hydroxypropyl--cyclodextrin) and the concentrationof cyclodextrin and by environmental factors such as temperature and composition ofthe microbial indigenous population. The results obtained show that all the testedfactors influence the biodegradation kinetics. The best results were obtained with-cyclodextrin at a concentration near to its water solubility limit; moreover,biodegradation rate increases with temperature and different microbial strains showdifferent degradative activity and metabolic behaviour.     

Thermodynamics of aqueous sodium sulfate

The activity coefficient of saturated aqueous Na₂SO₄ is calculated from the properties of the solid and the infinitely dilute solution as well as the solubility. These values are compared with those given by the equation of Rogers and Pitzer which is based on the measured dependence of heat capacity upon molality together with other solution properties at low temperature. Excellent agreement is found from 30 to 280°C. Consequently the equation of Rogers and Pitzer is given an extended range of validity to saturated molality and to 280°C. The trend of solubility with temperature is discussed in relation to the C_p of solution.     

Studies on the electrical double layer structure at the water/air interface

Effective dipole moments (calculated from experimental data of surface tension and electric surface potential) of some homologous normal alcohols and carboxylic acid were found to vary linearly with the number of carbon atoms in the hydrocarbon chain. Values of effective dipole moments were used for the determination of the effective dipole moments of water molecules , and the dielectric permittivity of the water subphase (₁), as well as in the vicinity of the hydrophobic part of adsorbed molecule (₂). The latter was found to decrease with the increase of the hydrocarbon chain length. Knowing the effective dipole moment of surface water dipoles, the average orientation angle () of water molecules at the inteface was estimated. The calculated potential drop of water varies within the range –0.038 to –2.38 V for two extreme orientations of water dipoles at the surface.     

Effect of Temperature on The Solubility of α-Amino Acids and α,ω-Amino Acids in Water

The aqueous solubilities of glycine, dl-α-alanine (2-aminopropanoic acid), dl-α-aminobutyric acid (2-aminobutanoic acid), dl-α-norvaline (2-aminopentanoic acid), dl-α-norleucine (2-aminohexanoic acid), β-alanine (3-aminopropanoic acid), γ-aminobutyric acid (4-aminobutanoic acid), 5-aminovaleric acid (5-aminopentanoic acid), and 6-aminocaproic acid (6-aminohexanoic acid) were determined from 293.15 to 323.15 K at intervals of 5.00 K using the gravimetric method. The temperature dependence of the solubility of α-amino acids and α,ω-amino acids in water is well described by the van’t Hoff equation. Linear van’t Hoff plots were used to determine the differential enthalpy of solution. The results obtained are compared with reported values in literature and are discussed in terms of the position of the ionic groups in the hydrocarbon chain.     

Micellar solubilization of biopolymers in hydrocarbon solvents. ii. the case of horse liver alcohol dehydrogenase

The chemical characterization of horse liver alcohol dehydrogenase solubilized in isooctane via reverse micelles formed by the anionic surfactant di (2-ethyl-hexyl) sodium sulfosuccinate (AOT) and water (0.6 to 4% v/v) is presented. The enzyme’s catalytic activity toward acetaldehyde reduction is markedly dependent upon w0 = [H2O]/[AOT], and upon the pH of the stock aqueous solution (pHst), from which the hydrocarbon enzyme solution is prepared. Kinetically, the micellar solution appears to follow a normal Michaelis-Menten behavior, with a turnover number which, under the optimal conditions (w0 = 42, pHst = 8.8), appears to be higher than in bulk water. The affinity between enzyme and NADH, as judged from direct binding studies (quenching of the protein fluorescence), is much reduced with respect to water if concentrations refer to the water pool of the micelles, and comparable to water if concentrations refer to the overall volume (hydrocarbon plus water pool). Also, the Km values are much higher if concentrations refer to the water pool. Ultraviolet absorption studies show that the aromatic chromophores are not significantly perturbed on going from a water solution to the micellar solution. The essentially aqueous environment of the protein in the reverse micelles is confirmed by fluoresence studies. Circular dichroism studies show that the enzyme’s conformation in the micelles is similar to that in water; however, under certain conditions, small but significant changes of the main chain folding seem to occur, which do not impair enzymatic activity. The spectroscopic properties of NADH in the hydrocarbon phase (fluorescence and circular dichroism) are also investigated. The potential of the LADH-NADH system for technical applications (oxidoreduction of lipophylic substrates) is discussed.     

Effects of dissolved electrolytes on the solubility and partial molar volume of helium in water from 50 to 400 atmospheres at 25°C

The solubility of helium in water and aqueous CsCl, NaCl and MgCl₂ solutions at concentrations up to 3.380 molal has been measured at 50 atm intervals from 50 to 400 atm at 25°C. Setschenow coefficients for helium are practically invariant with pressure in each solution, decrease significantly with increasing electrolyte concentration and vary with the type of electrolyte in a fashion identical to that observed for the low pressure solubilities of other gases. The pressure dependence of the helium solubility in each solution follows a form of Henry's law in which the helium partial molar volume at infinite dilution \(\bar V^{_{He}^o } \) is independent of pressure. Values of \(\bar V^{_{He}^o } \) , computed from Henry's law, are smaller for the electrolyte solutions than for water and vary systematically with the type and concentration of dissolved electrolyte. This result is explained qualitatively in terms of ion hydration and its influence on the ability of the intrinsic configurational volume in each liquid to accommodate the relatively small helium molecules. It is concluded that intrinsic solvent structure is an important factor governing the partial molar volume of helium and the pressure dependence of helium solubility in water and aqueous electrolytes.     

多环芳烃水中溶解度的理论计算

建立了计算多环芳烃水中溶解度的数学表达式，用量子化学方法计算了7个多环芳烃的水中溶解度，计算结果与实验测定结果相符合．多环芳烃处于水体内体系状态能量愈高，其溶解度愈小，多环芳烃中的碳氢基团越多，溶解度越小．此时体系中的溶质呈单分子态，而不是聚集态．     

Solubility of light hydrocarbons and their mixtures in pure water under high pressure

New solubility data of methane, ethane, n-butane and their mixtures in pure water are obtained at 344.25 K, from 2.5 to 100 MPa. The results agree well with those of the literature in the case of pure hydrocarbons in water, but differ significantly for hydrocarbon mixtures. In contrast to the conclusion reached by Amirijafari and Campbell [B. Amirijafari, J. Campbell, Solubility of gaseous hydrocarbon mixtures in water, Soc. Pet. Eng. J. (1972) 21–27.], the experimental solubility data of methane–ethane mixtures shows an ideal solution behavior, while the solubility data of methane–n-butane mixtures shows a weaker non-ideality than that observed by McKetta and Katz [J.J. McKetta, D.L. Katz, Methane–n-butane–water system in two-and three-phase regions, Ind. Eng. Chem. 40 (1948) 853–863]. The pure hydrocarbon solubility data are satisfactorily correlated using the Soreide and Whitson modification [I. Soreide, C.H. Whitson, Peng–Robinson predictions for hydrocarbons, CO2, N2, and H2S with pure water and NaCl brine, Fluid Phase Equilib. 77 (1992) 217–240] of the Peng–Robinson equation of state.     

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.     

Aggregation of cyclodextrins: An explanation of the abnormal solubility ofβ-cyclodextrin

-,- and -Cyclodextrins have been shown to exist as aggregates in solution bound together by a network of hydrogen bonds. Removal of this network by ionisation of the hydroxyl groups leads to a greatly increased solubility and removal of aggregation. The presence of aggregates in solution of structure breaking solutes in which the solubility of-cyclodextrin is greatly enhanced, leads to a proposal that the abnormally low solubility of-CD may be explained by the presence of aggregates and the unfavourable interaction of these aggregates with the hydrogen bonded structure of water.     

Solubility of l-tartaric Acid in Ethanol, Propanol, Isopropanol, n-Butanol, Acetone and Acetonitrile

The solubility of l-tartaric acid was measured in ethanol, propanol, isopropanol, n-butanol, acetone and acetonitrile in the temperature range 281.15 and 324.25 K under atmospheric pressure by a gravimetric method. The solubility of l-tartaric acid in those selected solvents increases with increasing temperature. The apparent molar enthalpies of solution of l-tartaric acid in the selected solvents were estimated from the solubility data. The solubility results were correlated with the van’t Hoff equation, the modified Apelblat equation, and the λh equation. Agreement with the experimental data was very good in all cases. The experimental results could be useful for optimizing the purification process of l-tartaric acid in industry.     

ON THE PHENOMENOLOGICAL THERMODYNAMICS OF HYDROPHOBIC BONDING

This paper is a review of the points of view of Frank and Evans, Shinoda and the author regarding the hydrophobic hydration of hydrocarbon molecules, with the emphasis on the contribution of the author. It is demonstrated that the enthalpic free energy change, due to the interactions between the hydrocarbon molecules and water, is compensated by the entropic free energy change, due to the ordering caused by the hydrocarbon molecules in the neighboring water molecules. Further, it is shown that the free energy change due to the iceberg formation is negative. Some simplifying assumptions make it possible to conclude that the absolute value of the free energy for iceberg formation can be as large as 1/3 of the free energy change associated with the formation of a cavity. The thermodynamic approach employed can also explain the existence of a minimum in the temperature dependence of the hydrocarbon solubility in water.     

Study of the Hyflon AD80 perfluorinated copolymer by inverse gas chromatography

The perfluorinated copolymer of tetrafluoroethylene and perfluoromethoxydioxole, Hyflon® AD80x, is investigated by inverse gas chromatography. C₅–C₁₃ n-alkanes are used as sorbates, for which the specific retention volume, the solubility coefficient at infinite dilution, and the excess thermodynamic functions are calculated in the temperature range 30–115°C. The solubility coefficients of the hydrocarbons in the studied polymer are shown to be lower than those in amorphous Teflons AF1600 and AF2400, a finding that is consistent with the difference between the glass-transition temperatures of these polymers. The correlation between excess partial molar enthalpies and critical volumes of n-alkanes testifies that the upper limit for the size of the free-volume element in this polymer is 613 ų. Mixing of n-alkanes with Hyflon AD80 is thermodynamically disadvantageous (\(\bar G_1^{E,\infty } \) > 0) and becomes even less advantageous with an increase in the size of hydrocarbon molecules. Excess entropy mainly contributes to the high values of excess free energy, thus indicating a higher order in the system containing the glassy polymer than that in systems in which the polymer occurs in the rubberlike state.     

Is there a region of highly structured water around a nonpolar solute molecule?

Published measurements of water proton chemical shifts for dilute solutions of alcohols and other hydrocarbon derivatives surprisingly seem to imply that hydrophobic groups enhance water structure near 0°C but disrupt it at elevated temperatures. A model is presented which allows these observations to be rationalized and is consistent with experimental values of enthalpies and heat capacities of solution of hydrocarbon gases. It requires the assumption that hydration-shell H-bonds have higher bond-breaking enthalpies and entropies than those in bulk water. These quantities are evaluated from available thermochemical data. Using the corresponding free energies of bond breaking, it is then calculated that the fraction of broken H-bonds is larger in the hydration shell than in the bulk liquid even at temperatures near the freezing point. The Model does not invoke formation of extended ordered regions that could be described as icebergs and that melt when the solutions are heated.