0000000000255927
AUTHOR
Americo Inglese
Excess free energy, enthalpy and entropy of surfactant-surfactant mixed micelle formation
Enthalpies of dilution and osmotic coefficients of sodium decylsulfate (NaDeS)-dodecyldimethylamine oxide (DDAO) mixtures in water were determined at 298 and 310 K, respectively. From the enthalpies of dilution, the apparent and then the partial molar relative enthalpies of the surfactant mixtures were calculated. From the osmotic coefficients, calculated at 298 K, the non-ideal free energies were derived. The latter were combined with the partial molar relative enthalpies to obtain the non-ideal entropies. From the apparent molar properties, using a previously reported approach, the excess thermodynamic properties for the surfactant-surfactant mixed micelle formation in water were evaluate…
Thermodynamic Studies of Sodium Dodecyl Sulfate–Sodium Dodecanoate Mixtures in Water
Abstract Conductivity, density, heat capacity, enthalpy of dilution, and osmotic coefficient measurements of water–sodium dodecyl sulfate (NaDS)–sodium dodecanoate systems were carried out as functions of the surfactants total molality ( m t ) at different mole fractions ( X NaDS ). From conductivity data, the critical micelle concentration (cmc) and the degree of ionization of the micelles (β) were calculated. The cmc vs X NaDS profile deviates negatively from that predicted on the basis of the Clint approach, while the β vs X NaDS profile deviates positively from the line correlating the values for pure surfactants. At a given mole fraction, the profiles of all the investigated properties…
Group contributions to the infinite dilution partial molar volumes of alkanes, alcohols, and glycols in polar organic solvents
Densities of binary mixtures of polar organic solvents with alcohols were measured at 25‡C. The solvents studied were N,N-dimethylformamide, dimethylsulfoxide, and formamide while alcohols were butanol, pentanol, hexanol, and 1,4-butanediol. Density measurements of hydrocarbons (from pentane to dodecane and some heptane isomers) + N,N-dimethylformamide were also performed. From these data the apparent molar volumes of alcohols and hydrocarbons as functions of concentration were calculated. The standard partial molar volumes were obtained by extrapolation to infinite dilution and are discussed in terms of group contributions.
Standard partial molar volumes of alcohols in aqueous dodecyltrimethylammonium bromide solutions
Density measurements of water-dodecyltrimethylammonium bromide (DTAB)-alcohol ternary systems as a function of alcohol and surfactant concentrations were carried out at 25°C. The alcohols were propanol (PrOH), 2-propanol (2-PrOH) and hexanol (HexOH). The apparent molar volume Vϕ,R of alcohols have been calculated and the standard (infinite dilution) partial molar volumes of alcohols V R at each surfactant concentration were obtained by means of a least squares fit of Vϕ,R vs. the alcohol concentration. The V R vs. surfactant concentration curves have been rationalized in terms of the partial molar volume of alcohol in the aqueous V f and the micellar V b phases and the distribution constant…
Enthalpy of Solution of Nonionic Solutes in Organized Systems
The standard enthalpies of solution of alcohols in micellar solutions of dodecyltrimethylammonium bromide were obtained by direct measurements and by enthalpies of mixing. The observed trends were analyzed with a previously reported model. From the resulting equations, the distribution constant, standard enthalpy of transfer from aqueous to the micellar phase and the standard enthalpy of solution in micellar phase can be calculated at the same time using a linear least-squares analysis. The model seems to hold well also in the case of short chain surfactants and microheterogeneities in spite of the fact that the micellization equilibrium is treated as a pseudo-phase transition.
Mass action model for solute distribution between water and micelles. Partial molar volumes of butanol and pentanol in dodecyl surfactant solutions
The densities of 1-butanol and 1-pentanol were measured in aqueous solutions of dodecyltrimethylammonium bromide and dodecyldimethylamine oxide and the partial molar volumes at infinite dilution of the alcohols in aqueous surfactants solutions were obtained. The observed trends of this quantity as a function of the surfactant concentration were rationalized using a mass-action model for the alcohol distribution between the aqueous and the micellar phase. At the same time, the model was revised to account for the alcohol effect on the surfactant micellization equilibrium. The partial molar volume of alcohols in the aqueous and in the micellar phases and the ratios between the binding constan…
Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solute in Micellar Solutions
Density measurements of pentanol (PentOH)−dodecyltrimethylammonium bromide (DTAB)−water mixtures as functions of both alcohol and surfactant (mS) concentrations were carried out at 0.1 MPa from 45 to 75 °C and at 19 MPa from 25 to 130 °C. The standard (infinite dilution) partial molar volumes and expansibilities of DTAB in water and the corresponding properties in the micellar phase were calculated from the experimental data. As far as PentOH in DTAB micellar solutions is concerned, with the exception of the standard partial molar volume (V°R) data at 130 °C and 19 MPa, all the V°R vs mS trends are monotonic curves with mS. The data of V°R as a function of mS were treated by means of an equ…
Thermodynamic Properties of Sodium n-Alkanecarboxylates in Water and in Water + Cyclodextrins Mixtures
Densities and heat capacities of water−substrate, water−cyclodextrin, and water−substrate−cyclodextrin systems were determined at 298 K. The substrates studied are sodium n-alkanecarboxylates (CnCOONa) (from sodium acetate to sodium decanoate) and the cyclodextrins are hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin, (HP-β-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD). The apparent molar volumes and heat capacities of CnCOONa in water were calculated as functions of concentration. The standard partial molar properties agree with those obtained by using the additivity rule. HP-β-CD essentially does not affect the thermodynamic properties of C1COON…
Volumes and heat capacities of anionic-nonionic surfactant mixtures
Density, heat capacity and surface tension measurements of sodium decylsulfate (NaDeS)-dodecyldimethylamine oxide (DDAO)-water mixtures were carried out as functions of the surfactants total molality mt at fixed stoichiometric mixture compositions XNaDeS. From the surface tension data, the critical micelle concentration of NaDeS-DDAO mixtures as a function of XNaDeS were obtained. From density and heat capacity data, the apparent molar volume VΦ,2 and heat capacity CΦ,2 of NaDeS-DDAO mixtures in water were calculated, respectively. At a given mole fraction, VΦ,2 and CΦ,2 monotonically increases and decreases, respectively, with increasing mt. However, anomalies were observed at XNaDeS=0.1 a…
Apparent molar volumes of 1-pentanol in water fromT=298 K toT=413 K atp=0.1 MPa andp=19 MPa
Abstract Densities of 1-pentanol aqueous solutions were measured by using a vibrating tube densimeter especially designed and equipped to perform accurate measurements from ambient conditions up toT=423 K andp=80 MPa. The densimeter was tested by measuring densities of NaCl (aq). A comparison with the most reliable literature data showed very good agreement with differences lower than (0.03 and 0.1) kg·m−3for molalities below and above 0.5 mol·kg−1, respectively. From the density measurements, the apparent molar volumes of 1-pentanol in water,Vφwere determined as a function of molalitymat temperatures fromT=298 K toT=413 K atp=0.1 MPa andp=19 MPa. At a given temperature and pressure, and pa…
Enthalpies of solution and dilution of butanol and pentanol in dodecyltrimethylammonium bromide micellar solutions
The enthalpies of solution and of dilution of 1-butanol and 1-pentanol were measured in micellar solutions of dodecyltrimethylammonium bromide by systematically changing the concentration of alcohols and surfactant. The enthalpies of solution at infinite dilution of alcohols at each surfactant concentration were evaluated from a linear plot. This quantity increases with surfactant concentration (up to 0.8m) with a curvature which depends on the alcohol alkyl chain length. The difficulties arising for a quantitative treatment of both the enthalpies of dilution and of solution at finite alcohol concentrations are discussed. The dependence on the surfactant concentration of the standard enthal…