0000000000060035
AUTHOR
R. De Lisi
showing 58 related works from this author
Thermodynamic studies of octyltrimethylammonium chloride in water
1992
Densities, heat capacities, enthalpies of dilution at 298 K and osmotic coefficients at 310 K of octyltrimethylammonium chloride were measured as functions of concentration. From the experimental data, the partial molar volumes, heat capacities, relative enthalpies, nonideal free energies and entropies at 298 K were derived as functions of concentration. A comparison between the above data and those of dodecyltrimethylammonium chloride reported in the literature shows that the increase of the alkyl chain length shifts the apparent molar volumevs. concentration curves towards greater values and the heat capacity, relative enthalpy and free energyvs. concentration curves towards smaller value…
Calorimetric and Volumetric Investigations of the Effect of the Hydrophobicity of the Surfactant on the Binding between (Ethylene oxide)13-(propylene…
2004
The enthalpy and the volume of transfer (DeltaY(t)) of the unassociated (ethylene oxide)(13)-(propylene oxide)(30)-(ethylene oxide)(13) (L64) from water to the aqueous sodium alkanoate solutions as functions of the surfactant concentrations (m(S)) were determined at 298 K. The surfactants studied are sodium hexanoate, sodium heptanoate, sodium octanoate, sodium undecanoate, and sodium dodecanoate. As a general feature, for the short alkyl chain surfactants, DeltaY(t) describes an S-shaped curve in the range of m(S) analyzed whereas for the more hydrophobic surfactants the DeltaY(t) vs m(S) trends exhibit maxima which appear at ms values very close to the critical micellar concentration in w…
Thermodynamics of transfer of some nitroalkanes from aqueous to dodecyltrimethylammonium bromide micellar phases
1988
Abstract The enthalpies of mixing of some aqueous n-nitroalkane solutions with dodecyltrimethylammonium bromide micellar solutions were determined. The experimental data were treated by using a previously reported approach giving the enthalpies of transfer of solute from the aqueous to the micellar phases and the distribution constant of solute between the two phases at the same time. From these, the standard thermodynamic quantities of transfer (ΔtrfG°, ΔtrfH° and ΔtrfS°) are derived. In order to study the effect of the nature of both the solvent and the head group of solute, these properties are compared with those from water to octane and with those of alcohols and nitriles from aqueous …
Binding between (Ethylene Oxide)13−(Propylene Oxide)30−(Ethylene Oxide)13 and Sodium Decanoate. Volume, Enthalpy, and Heat Capacity Studies
2002
Volume, enthalpy, and heat capacity of transfer (ΔYt) of (ethylene oxide)13−(propylene oxide)30−(ethylene oxide)13 (L64), at some concentrations, from water to the aqueous sodium decanoate (NaDec) solutions as functions of the surfactant concentration (mS) were determined at 298 K. The copolymer was studied in both the unassociated and associated forms. For a given L64 concentration (mC), the ΔYt vs mS profiles for the volume and the enthalpy are equal but different from that of the heat capacity because the latter contains also the relaxation terms. The experimental data were analyzed by assuming the distribution of L64 between the aqueous and the micellar phases and the shift of micelliza…
Thermodynamic properties and conductivities of some dodecylsurfactants in water
1988
Densities, heat capacities, enthalpies of dilution, osmotic coefficients and conductivities are reported for dodecylamine hydrochloride, dodecyldimethylammonium and dodecyltrimethylammonium chloride in water over a wide range of concentration. The last two properties were also measured for dodecyltrimethylammonium bromide. From the thermodynamic data partial molar volumes, heat capacities and relative enthalpies and nonideal free energies and entropies were derived as a function of the surfactant concentration. The cmc's and degree of counterion dissociation were also calculated from the transport properties. It is shown that the trends of volumes, enthalpies, free energies and entropies ar…
Heat capacities, volumes and solubilities of pentanol in aqueous surfactant solutions
1989
Apparent molar heat capacities and volumes of pentanol (PentOH) 0.05m in dodecyltrimethylammonium chloride (DTAC), dodecyldimethylammonium chloride (DDAC) and dodecylamine hydrochloride (DAC) micellar solutions were measured at 25°C. They were assumed to approach the standard infinite dilution values and rationalized by means of previously reported equations. The distribution constant between the aqueous and the micellar phase and heat capacity and volume of pentanol in both phases were thus derived. The results show that the presence of methyl groups on the surfactant head group does not appreciably influence the apparent molar volume and heat capacity of pentanol in micellar phase and the…
Energetics of sodium dodecylsulfate-dodecyldimethylamine oxide mixed micelle formation
1994
Enthalpies of dilution and osmotic coefficients of the sodium dodecyl-sulfate (NaDS)-dodecyldimethylamine oxide (DDAO) mixtures in water have been measured at 25 and 37°C, respectively. From the enthalpies of dilution the apparent molar relative enthalpies LΦ were calculated. The change of the LΦ vs. total molality mt profiles with the mole fraction reflects the variation of the ionic character of the mixed micelles. From the osmotic coefficients the nonideal free energy G2ni were calculated. By combining G2ni with the partial molar relative enthalpies, the nonideal entropies TS2ni were determined. At a given mole fraction, G2ni and TS2ni values are decreasing and increasing respectively, t…
Excess free energy, enthalpy and entropy of surfactant-surfactant mixed micelle formation
1996
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…
Heat Capacity of Transfer of (Ethylene oxide)13-(propylene oxide)30-(ethylene oxide)13 from Water to the Aqueous Anionic Surfactant Solutions at 298 …
2004
Heat capacities of transfer (ACpt) of unimeric (ethylene oxide)(13)-(propylene oxide)(30)-(ethylene oxide)(13) from water to the aqueous surfactant solutions as functions of the surfactant concentrations (m(S)) were determined at 298 K. The surfactants investigated are sodium hexanoate, sodium heptanoate, sodium octanoate, sodium undecanoate, and sodium dodecanoate. For short alkyl chain surfactants, the profiles of the DeltaCp(t) versus ms curves show maxima and minima; for long alkyl chain surfactants, the maximum becomes sharper and moved to lower ms values whereas the minimum tends to disappear. These experimental trends are different from those of the enthalpy in agreement with the fac…
A thermodynamic study to evidence the alpha,omega-dichloroalkane/ block copolymer mixed aggregates formation: effect of the copolymer architecture.
2006
Abstract The thermodynamics of α , ω -dichloroalkanes in aqueous solutions of (ethylene oxide)11(propylene oxide)16(ethylene oxide)11 (L35) and (propylene oxide)8(ethylene oxide)23(propylene oxide)8 (10R5) was determined at 298 and 305 K. Modeling the experimental data allowed to calculate the standard free energy ( Δ G D o / w ) and the volume ( Δ V D / w ) for the additive–copolymer mixed aggregates formation per additive molecule. Δ G D o / w for Cl2CH2 and Cl2(CH2)2 evidenced that the process is controlled by the forces exercising between the chlorine atoms and the OH groups of the copolymer micelles protruded into the aqueous phase. Cl2(CH2)3 experiences both the hydrophilic and hydrop…
Thermodynamics of Aqueous Poly(ethylene oxide)−Poly(propylene oxide)−Poly(ethylene oxide)/Surfactant Mixtures. Effect of the Copolymer Molecular Weig…
2004
A calorimetric study was performed to focus attention on the interactions between copolymers and anionic surfactants in aqueous solutions. Three aspects were analyzed: (1) the hydrophobicity of the surfactant, (2) the change of the copolymer molecular weight, and (3) the nature of the hydrophilicity of the copolymer. To this purpose, the family of sodium alkanoates (sodium octanoate through sodium dodecanoate) and the triblock copolymers EO76PO 29EO76 (F68), EO103PO39EO 103 and EO132PO50EO132 were investigated. Comparing F68 and EO13PO30EO13 (L64), previously studied by us, provided information on the effect of the copolymer hydrophilicity. The experimental data were analyzed by means of a …
Thermodynamic properties of water-β-cyclodextrin-dodecylsurfactant ternary systems
1995
Densities, heat capacities and conductivities of water-surfactant-β-cyclodextrin (β-CD) ternary systems were determined at 25°C. The surfactants studied were sodium dodecylsulfate (NaDS) and dodecyltrimethylammonium bromide (DTAB). From conductivity data, apparent critical micelle concentrations (cmc*) and degree of ionization of micelles were obtained at a fixed β-CD concentration (mCD). From the cmc* value and that in water (cmc) the stoichiometry of the surfactant-β-CD complex was calculated. At a given mCD, the apparent molar volume Vϕ,CD and heat capacity Cϕ,CD of β-CD in the two surfactants were calculated as functions of surfactant concentration mS. For both NaDS and DTAB, Vϕ,CD incr…
Binding of Short Alkyl Chain Surfactants to the (Ethylene oxide)13−(Propylene oxide)30−(Ethylene oxide)13and (Ethylene oxide)75−(Propylene oxide)30−(…
2002
The enthalpy of transfer (ΔHt) of neutral copolymers, at a fixed and low concentration ca. 10-3 mol kg-1, from water to the aqueous surfactant solutions as a function of the surfactant concentration (fSmS) was determined at 25 °C. The surfactants studied are sodium octanoate, sodium decanoate, N-octylpyridinium chloride (OPC), and N,N-dimethyloctylamine-N-oxide (ODAO). The copolymers are (ethylene oxide)13−(propylene oxide)30−(ethylene oxide)13 (L64) and (ethylene oxide)75−(propylene oxide)30−(ethylene oxide)75 (F68). The two copolymers show different hydrophilic−hydrophobic ratios, the larger being for F68. As a general feature, the shape of the ΔHt vs fSmS curve depends on the nature of t…
Thermodynamic Behavior of Non-Ionic Tri-block Copolymers in Water at Three Temperatures
2006
Apparent molar volumes (V Φ) of aqueous solutions of some copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, were determined as functions of concentration at three temperatures. Viscosity measurements were also carried out on some of these systems. The effects studied include how the molecular architecture and the molecular weight affect the aggregation of the copolymer, keeping constant the EO/PO ratio. Modeling of the volumetric data yielded the partial molar volume of the copolymer in the standard (V°) and the aggregated (V M) states, as well as the equilibrium constant for micellization and the aggregation number. Analysis of the viscosity data supported the insigh…
Thermodynamic Studies of Sodium Dodecyl Sulfate–Sodium Dodecanoate Mixtures in Water
1996
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…
Volumes of aqueous block copolymers based on poly(propylene oxides) and poly(ethylene oxides) in a large temperature range: A quantitative description
2006
The focus of this paper was on a quantitative comprehension of temperature effect on the volumes of aqueous di-block and triblock copolymers, based on propylene oxide (PO) and ethylene oxide (EO) units. To this purpose, literature data dealing with (EO316PO94 + water) and (EO13PO30EO13 + water) mixtures were analyzed. The volume vs. temperature trends were rationalized on the basis of the (unimers + aggregate) equilibrium by taking into account the temperature effect on both the partial molar volumes of the unimeric and the aggregated copolymer as well as the equilibrium constant of micellization. The analysis extended to the expansibility allowed to quantify the contribution for the shift …
Volumes of Polar Additives in Aqueous Solutions of the Poly(ethylene oxide)13−Poly(propylene oxide)30− Poly(ethylene oxide)13 Triblock Copolymer at 2…
1999
Density measurements of poly(ethylene oxide)13−poly(propylene oxide)30−poly(ethylene oxide)13 (L64)−water and alcohol−L64−water systems were carried out at 293 and 301 K. The alcohols studied are propanol to pentanol and 2,2,2-trifluoroethanol (F3EtOH) to 2,2,3,3,4,4,4-heptafluorobutanol (F7BuOH). From the experimental data of the water−L64 binary system as functions of L64 concentration (mC), the partial molar volumes of L64 in the standard state and in the aqueous and micellar phases were calculated. At both temperatures L64 micelle is formed by a core of pure polypropylene oxide units and a hydrated shell of poly(ethylene oxide) units. In the case of the ternary systems, the apparent mol…
Thermodynamics of Solubilization of Pentanol in Sodium Dodecyl Sulfate-Dodecyldimethylamine Oxide Mixed Micelles
1994
Abstract Heat capacity and density measurements of pentanol (PeOH)-sodium dodecyl sulfate (NaDS)-dodecyldimethylamine oxide-water mixtures were carried out at 0.03 m PeOH as a function of the total surfactants concentration (mc) at different ratios (XNaDS). From experimental data, the apparent molar volumes (VΦ,R) and heat capacities (CΦ,R) of PeOH in the surfactants mixture solutions were calculated. As a general feature, at a given mixture composition, VΦ,R increases monotonically with mt as observed in pure surfactants. In the cases of XNaDS = 0.1 and 0.3, VΦ,R drops at about 0.1 and 0.15 mt respectively. The decreasing CΦ,R VS mt curve shows peculiarities which were ascribed to the pres…
Aqueous nonionic copolymer-functionalized laponite clay. A thermodynamic and spectrophotometric study to characterize its behavior toward an organic …
2006
The affinity of functionalized Laponite clay toward an organic material in the aqueous phase was explored. Functionalization was performed by using triblock copolymers based on ethylene oxide (EO) and propylene oxide (PO) units that are EO(11)PO(16)EO(11) (L35) and PO(8)EO(23)PO(8) (10R5). Phenol (PhOH) was chosen as organic compound, which represents a contaminant prototype. To this purpose, densities and enthalpies of mixing as well as PhOH UV-absorption spectra were determined. The enthalpy and the spectrophotometry revealed PhOH-Laponite interactions whereas the volume did not. It emerged that the area occupied by PhOH on the Laponite surface is equal to that computed from the partial m…
Enthalpies of transfer of pentanol from water to sodium dodecylsulfate-dodecyl-dimethylamine oxide-water mixtures
1994
At a given surfactant-surfactant ratio, the enthalpies of transfer ΔH (W→W+S) of pentanol 0.03m from water to sodium dodecylsulfate (NaDS)-dodecyldimethylamine oxide-water mixtures as functions of the surfactants mixture concentration (m t) were determined. ForX NaDS=0.9, ΔH (W→W+S) increases monotonically withm t such as observed for pure surfactants. ForX NaDS=0.12 and 0.3, ΔH (W→W+S) increases withm t up to 0.12m beyond which it decreases withm t. AtX NaDS=0.6, two monotonic curves can be distinguished in the ΔH (W→W+S)vs. m t trend. Experimental data were fitted through an equation previously reported for additives in pure surfactants derived by assuming the pseudo-phase transition mode…
Thermodynamics of transfer of polar additives from the aqueous to the dodecylsurfactant micellar phases
1990
The enthalpies of transfer from water to aqueous surfactant solutions, ΔH(W→W+S), of polar additives have been determined as a function of the surfactant concentration at fixed additive concentration. The surfactants used are sodium dodecylsulfate (NaDS), dodecyltrimethylammonium bromide and dodecyldimethylamine oxide (DDAO). The additives used are iso-butanol t-butanol, butoxyethanol, phenol, benzene, tributylphosphine oxide (TBPO), octyldimethylphosphine oxide (ODPO), octydimethylamine oxide (ODAO), DDAO and NaDS. A maximum was observed in the plots of ΔH(W→W+S) vs. fsms curves for ODPO and ODAO in NaDS while a small minimum was observed for TBPO. The experimental data are rationalized on…
Laponite clay in homopolymer and tri-block copolymer matrices
2007
Macromolecule/laponite nanomaterials were studied by DSC and X-ray diffraction techniques. The matrices are poly(ethylene) glycols at various molecular masses and poly(ethylene oxides)-poly(propylene oxides)-poly(ethylene oxides) tri-block copolymers. The latter were tuned by modulating the molecular masses, at constant hydrophilic/hydrophobic ratio, and the hydrophilicity. For all the investigated systems, the enthalpy of melting (ΔH m) is nearly constant up to a given composition thereafter it increases monotonically reaching the value of the pure macromolecule. We proposed a model to interpret the DSC data. Briefly, it was invoked a mechanism of interaction following which some segments …
Polymer−Surfactant Interactions. A Quantitative Approach to the Enthalpy of Transfer of Poly(Ethylene Glycol)s from Water to the Aqueous Sodium Perfl…
2000
The enthalpy of transfer (ΔHt) of nonionic polymers at a fixed concentration from water to aqueous substrate solutions as a function of the substrate concentration (fSmS) was determined. The substrates studied are sodium perfluorobutanoate to sodium perfluorooctanoate, and the polymers are poly(ethyleneglycol)s with molecular weights of 400 and 35 000. For the PEG 400-sodium perfluoroheptanoate−water systems, measurements were also performed at some polymer compositions. As a general feature, the enthalpy of transfer steeply changes with fSmS, reaching a maximum beyond which it decreases, tending to level off. A qualitative analysis of the enthalpy data assigned the steep increase of ΔHt to…
Thermodynamic and19F NMR studies of antimony trifluoride in water
1993
Densities, specific heat capacities per unit volume and enthalpies of dilution at 25°C and osmotic coefficients at 37°C were measured for antimony trifluoride in water as functions of concentration. From the first three properties the apparent and partial molar volumes, heat capacities and relative enthalpies were derived. As well, pH measurements in water at 25°C and19F NMR spectra in water and methanol at 33°C were also carried out. All the thermodynamic properties together with the chemical shifts abruptly change in the very dilute concentration region (<0.1m) and, then, tend to a constant value. These trends have been rationalized through a simple model based on an equilibrium of dissoc…
Heat Capacity Study to Evidence the Interactions between Cyclodextrin and Surfactant in the Monomeric and Micellized States
2003
The heat capacities of transfer (ΔCpt) of hydroxypropyl-α-cyclodextrin and hydroxypropyl-γ-cyclodextrin (0.05 mol kg-1) from water to aqueous solutions of sodium hexanoate, sodium decanoate, and so...
Thermodynamics ofN,N,N-octylpentyldimethyl-ammonium chloride in water-urea mixtures
1997
Specific conductivities, densities, heat capacities, and enthalpies of dilution at 25‡C were measured forN,N,N-octylpentyldimethylammonium chloride (OPAC) in water-urea mixtures at various urea concentrations mu as functions of the surfactant concentration ms. From conductivity data, the cmc and the degree of the counterion dissociation Β of the OPAC micelles were calculated. The cmc increases linearly with increasingm u while Βvs. mu is a smooth concave curve. From the experimental thermodynamic data, the apparentY Φ and partialY 2 molar properties (volumes, heat capacities, and relative enthalpies) are derived as functions of mu andm s . The effect of urea on the dependences of the differ…
Standard partial molar volumes of alcohols in aqueous dodecyltrimethylammonium bromide solutions
1990
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
1989
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.
Polyethylene glycol/clay nanotubes composites
2012
Nanocomposites of poly(ethylene) glycol (PEG) 20000 filled with clay nanotubes (HNTs) were prepared. The thermal properties obtained from thermogravimetry and differential scanning calorimetry were correlated to the morphology imaged by scanning electron microscopy. Low amounts of HNTs generate compact structure while large amounts of HNTs create craters and voids. The decrease of polymer degradation temperature in the presence of large amount of nanoclay (ca. 80 wt%) is a consequence of the morphology at the mesoscale range. The thermal opposite effect observed in the HNTs low regime (up to ca. 20 wt%) is due to the gas entrapment into the nanoparticles lumen. The quantitative analysis of …
Mass action model for solute distribution between water and micelles. Partial molar volumes of butanol and pentanol in dodecyl surfactant solutions
1986
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…
Thermodynamic properties of some N-alkyl-N-methylpiperidinium chlorides and N-alkylpiperidine hydrochlorides in water
1993
Densities and heat capacities at 25[degrees]C were measured for N-octyl-, N-decyl- and N-dodecyl-N-methylpiperidinium chlorides and for N-octyl- and N-dodecylpiperidine hydrochlorides in water as functions of concentration. Enthalpies of dilution at 25[degrees]C and osmotic coefficients at 37[degrees]C of the N-methyl-N-alkylpiperidinium chlorides were also measured as functions of concentration. The partial molar volumes, heat capacities, relative enthalpies, nonideal Gibbs energies and entropies at 25[degrees]C were derived as functions of the surfactant concentration. By increasing the alkyl chain length of the surfactant, both the apparent molar volume vs. concentration curves are shift…
Volumes and compressibilities of pentanol in aqueous dodecyltrimethylammonium bromide solutions at 15, 25 and 35°C
1990
Ultrasonic velocities and densities of the water-dodecyltrimethylammonium bromide (DTAB)-pentanol (PentOH) ternary system were measured at 15, 25 and 35°C as a function of the surfactant and alcohol concentrations. The apparent molar volumes and isentropic compressibilities of PentOH were calculated. The standard partial molar volumes increase with surfactant concentration continuously whereas the standard partial molar isentropic compressibilities show sharp changes in slope at about 0.25 mol-kg−1 DTAB, which can be ascribed to a micellar structural transition. The volume data for alcohol in micellar solutions were treated by a model reported for the distribution of polar additives between…
Aqueous block copolymer-surfactant mixtures and their ability in solubilizing chlorinated organic compounds. A thermodynamic and SANS study.
2006
Within the topic of surfactant enhanced solubilization of additives sparingly soluble in water, volumetric, solubility, conductivity, and small-angle neutron scattering (SANS) experiments on mixtures composed of alpha,omega-dichloroalkane, surfactant, copolymer, and water were carried out at 298 K. The triblock copolymers (ethylene oxide)132(propylene oxide)50(ethylene oxide)132 (F108) and (ethylene oxide)76(propylene oxide)29(ethylene oxide)76 (F68) were chosen to investigate the role of the molecular weight keeping constant the hydrophilic/hydrophobic ratio. The selected surfactants are sodium decanoate (NaDec) and decyltrimethylammonium bromide (DeTAB) with comparable hydrophobicity and …
Thermodynamic properties of N-octyl- and N-dodecylnicotinamide chlorides in water
1990
Densities, heat capacities and enthalpies of dilution at 25°C and osmotic coefficients at 37°C were measured for N-octyl- and N-dodecylnicotinamide chlorides in water over an extended concentration region. Partial molar volumes, heat capacities, relative enthalpies and nonideal free energies and entropies at 25°C were derived as a function of the surfactant concentration. For both surfactants, plots of volumes, enthalpies and free energies vs. concentration are regular whereas those of heat capacities and entropies present anomalies at about 0.8 and 0.1m for the octyl and dodecyl compounds, respectively. Changes in the slope of a plot of osmotic coefficients times molality vs. molality were…
Volumes and compressibilities of pentanol in aqueous alkyltrimethylammonium bromide solutions at different temperatures
1990
Speed of sound and density properties of ternary water-tetradecyltrimethylammonium bromide-pentanol system at 15, 25 and 35°C and of water-hexadecyltrimethylammonium bromide-pentanol system at 25, 35 and 45°C were measured at fixed alcohol concentration as a function of surfactant concentration. The apparent molar volumes Vϕ,R and isentropic compressibilities Kϕ,RS of pentanol in micellar solutions as a function of the surfactant concentration show irregular behavior which depends on the alkyl chain length of the surfactant and tends to disappear with increasing temperature. These anomalies are ascribed to micellar transitions. For both surfactants at high concentrations, Vϕ,R decrease and …
N,N,N-Alkyloctyldimethylammonium Chlorides in Water: A Thermodynamic Investigation
1993
Abstract Specific conductivities, densities, heat capacities and enthalpies of dilution at 298 K and osmotic coefficients at 310 K were measured for N,N,N -octylbutyldimethylammonium, N,N,N -octylpentyldimethylammonium, and N,N -dioctyldimethylammonium chlorides in water as functions of concentration. From the specific conductivity data, the CMC and the degree of the counterion dissociation have been calculated. It is shown that additional CH 2 groups in the variable alkyl chain affect both CMC and β less than they do in the single chain surfactants. The partial molar volumes, heat capacities, relative enthalpies, nonideal free energies, and entropies at 298 K were derived as functions of t…
Polystyrene nanoparticles in the presence of (ethylene oxide)13(propylene oxide)30(ethylene oxide)13, N,N-dimethyloctylamine-N-oxide and their mixtur…
2008
Polystyrene nanoparticles were synthesized by emulsion polymerization of styrene. They were functionalized using the conventional surfactant N,N-dimethyloctylamine-N-oxide (ODAO), the tri-block copolymer (ethylene oxide)13(propylene oxide)30(ethylene oxide)13 (L64) and their mixtures. To this purpose, dynamic light scattering and calorimetric experiments were carried out and provided information consistent to each other. The L64 adsorption is Langmuir-type in the copolymer dilute regime and generates complex structures at larger concentrations. In the region where ODAO is in the unimeric state, the adsorption process is cooperative leading to hemi-micelle formation at the polystyrene nanopa…
Mass Action Model Applied to the Thermodynamic Properties of Transfer of Nonionic Copolymers from Water to the Aqueous Surfactant Solutions
2003
A thermodynamic model which enables the properties of aqueous copolymer/surfactant mixtures to be fit quantitatively was proposed. Namely, a relationship between the properties of transfer of the unassociated copolymer from water to the aqueous surfactant solutions (DeltaY(t)) and the surfactant concentration was derived. The model was based on the idea that AY, can be expressed in terms of the following contributions: (1) interaction between monomers of copolymer and surfactant, (2) displacement of the monomer-micelle equilibrium induced by the copolymer, (3) formation of the surfactant-copolymer aggregation complex, and (4) formation of the mixed micelles. Such a model was applied to most…
Enthalpies of mixing of some nitriles aqueous solutions with dodecylsurfactants micellar solutions
1988
The enthalpies of mixing of some n-nitriles (from acetonitrile to valeronitrile) aqueous solutions with dodecyltzimethylammonium bromide, sodium dodecylsulfate and dodecyltzimethylammonium oxide micellar solutions were determined. The measurements were performed by systematically changing the surfactant concentration at a given solute concentration. The experimental enthalpies were rationalized in terms of the standard enthalpy of transfer of solute from the aqueous to the micellar phase and of the distribution constant between the two phase. Information on the effect of the nature of the surfactant on the standard thermodynamic quantities of transfer(ΔG t o , ΔH t o , TΔS t o ) is reported…
Energetics of Water−Dodecyl Surfactant−Macrocyclic Compound Ternary Systems
1996
Enthalpies of dilution and osmotic coefficients of sodium dodecyl sulfate (NaDS) and dodecyltrimethylammonium bromide (DTAB) in water + 18-crown-6 ether (CR) and water + β-cyclodextrin (CD) at a fixed cosolvent concentration were measured at 298 and 310 K, respectively, as functions of the surfactant concentration (mS). Enthalpies of transfer ΔH (W → W + S) of CR (0.03 m) from water to NaDS and DTAB aqueous solutions as functions of mS were also determined at 298 K. From the enthalpies of dilution the apparent (LΦ,S) and partial (L2,S) molar relative enthalpies of both surfactants were calculated. Despite CR forms inclusion complexes with the anionic surfactant only, the L2,S vs mS profiles…
Adsorption of triblock copolymers and their homopolymers at laponite clay/solution interface. Role played by the copolymer nature
2009
The adsorption thermodynamics of copolymers, based on ethylene oxide (EO) and propylene oxide ( PO) units, at the laponite (RD) clay/liquid interface was determined at 298 K. The copolymer nature was tuned at molecular level by changing the hydrophilicity, the architecture and the molecular weight (Mw) keeping constant the EO/PO ratio. Polyethylene (PEGs) and polypropylene (PPGs) glycols with varying Mw and their mixture were also investigated to discriminate the role of the EO and the PO segments in the adsorption process. Enthalpies of transfer of RD, at fixed concentration, from water to the aqueous macromolecule solutions as functions of the macromolecule molality were determined. They …
Partial molar volumes and compressibilities of alkyltrimethylammonium bromides
1990
Density and ultrasound measurements were performed for dodecyl- and tetradecyltrimethylammonium bromide at 15, 25 and 35°C and for hexadecyltrimethylammonium bromide at 25, 35 and 45°C over a wide concentration region. From these and previously reported data, partial molar volumes and isentropic and isothermal compressibilities were derived as a function of the surfactant concentration. It is shown that by increasing the surfactant concentration the apparent molar volumes and compressibilities increase according to the expected behavior of surfactant solutions. However, anomalies are displayed in plots of apparent molar compressibility of tetradecyltrimethylammonium bromide and of the speed…
Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solu…
1996
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…
Excess enthalpies of solution of primary and secondary alcohols in dodecyldimethylamine oxide micellar solutions
1987
The excess enthalpies of solution with respect to water of some primary and secondary alcohols in dodecyldimethylamine oxide (DDAO) micellar solutions were measured by mixing aqueous solutions of alcohols with surfactant solutions. Standard free energies, enthalpies and entropies were obtained from the distribution of alcohols between aqueous and micellar phases. It is shown that thermodynamics of transfer of secondary alcohols from aqueous to the DDAO micellar phase differ slightly from those of their corresponding primary alcohols, that the additivity rule holds for free energies of transfer and that enthalpy and entropy display convex curves. The present data are compared with those from…
Thermodynamic Properties of Sodium n-Alkanecarboxylates in Water and in Water + Cyclodextrins Mixtures
1998
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
1995
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…
Heat capacities and volumes of suspensions in the presence of surfactants
2004
Abstract Density and heat capacity measurements of water–surfactant–silica ternary systems were carried out as functions of the silica and the surfactant concentrations at 298 K. From these properties, the apparent molar volume and heat capacity of the surfactant in a given water+silica mixture were evaluated. As well, the apparent specific volume and heat capacity of silica, at a given concentration, in the water+surfactant mixtures as functions of the surfactant concentration were calculated. Some surfactants (decyltrimethylammonium bromide, sodium octanoate, sodium decanoate, sodium dodecanoate, sodium decylsulfate, sodium perfluorooctanoate and N , N -dimethyldodecylamine- N -oxide) wer…
Heat capacities of butanol and pentanol in aqueous dodecyltrimethylammonium bromide solutions
1987
Heat capacities of the ternary systems water-dodecyltrimethylammonium bromide (DTAB)-butanol and water-DTAB-pentanol were measured at 25°C. The standard partial molar heat capacities of pentanol in micellar solutions show a maximum at about 0.35 mol-kg−1 DTAB that has been attributed to a micellar structural transition. This maximum tends to vanish by increasing the alcohol concentration and by decreasing the alcohol alkyl chain length; in the case of butanol it was not detected. The behavior of the standard partial molar heat capacities of alcohols in micellar solutions in the region above the cmc and below the structural transition was explained using a previously reported mass-action mod…
Thermodynamic Evidence of Cyclodextrin−Micelle Interactions
2002
The enthalpy of transfer (ΔHt) of hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), and β-cyclodextrin (β-CD) from water to the aqueous C6F13CO2Na and C7F15CO2Na solutions were determined in the pre- and post-micellar regions. The behavior of the macrocycles is system specific. Generally, the magnitude of the enthalpy is influenced by several factors: (1) the alkyl chain length of the surfactant, (2) the cyclodextrin cavity and its alkylation, (3) the interactions between the free cyclodextrin and the free surfactant, (4) the host−guest equilibrium constant, (5) the host/guest stoichiometry, and (6) the micelle-cyclodextrin (free and/or complexed) interactions…
Volumes and heat capacities of the aqueous sodium dodecanoate/sodium perfluorooctanoate mixtures in the presence of β-cyclodextrin
2003
Apparent molar volumes (VΦ) and heat capacities (CΦ) of the sodium dodecanoate (NaL)/sodium perfluorooctanoate (NaPFO) mixtures in the water/β-cyclodextrin (β-CD) solvent as functions of the surfactant total molality (mt) were determined at 25°C. For a given surfactant mixture, VΦ decreases with mt to ca. 0.05 mol kg−1 thereafter it increases tending to a constant value. CΦ displays a behaviour opposite to VΦ. The mt values where the apparent molar properties exhibit extrema are nearly coincident with the critical micellar concentrations determined by conductivity. An equation correlating VΦ to mt was derived by assuming that the equilibria for the 1∶1 surfactant/cyclodextrin complex format…
Volumes, heat capacities and solubilities of amyl compounds in decyltrimethylammonium bromide aqueous solutions
1989
Apparent molar heat capacities and volumes of amylamine (PentNH2) 0.02m, capronitrile (PentCN) 0.02m and nitropentane (PentNO2) 0.009m in decyltrimethylammonium bromide (DeTAB) micellar solutions, in water and in octane were measured at 25°C. By assuming that their concentration approaches the standard infinite dilution state, heat capacities and volumes were rationalized by means of previously reported equations following which the distribution constant between the aqueous and the micellar phase and heat capacity and volume of the additives in both phases are simultaneously derived. The present results are compared to those we have previously obtained for pentanol (PentOH). The thermodynam…
Temperature-controlled poly(propylene) glycol hydrophobicity on the formation of inclusion complexes with modified cyclodextrins. A DSC and ITC study.
2011
The study highlighted the main forces driving the formation of hydroxypropyl-cyclodextrins (HP-CDs) + poly(propylene) glycol 725 g mol(-1) inclusion complexes. The temperature parameter was chosen as the variable to modulate the hydrophobicity of the polymer, and consequently ITC experiments as functions of temperature as well as DSC measurements were done in a systematic way. The polymer is not included into HP-α-CD, it is strongly bound to HP-β-CD and it is floating in HP-γ-CD. The stability of the inclusion complexes is entropy controlled. The gain of the entropy is a unique result compared to the opposite literature findings for inclusion complexes based on polymers and CDs. This peculi…
Thermodynamics of Micellization of Sodium Alkyl Sulfates in Water at High Temperature and Pressure
2001
Apparent molar volumes VΦ,S were determined for sodium octyl, decyl, and dodecyl sulfates in water at 2 and 19 MPa from 25 to 130 °C. The shapes of VΦ,S vs the surfactant concentration curves depend on the surfactant alkyl chain, temperature and pressure. The standard partial molar volumes were calculated from data in the premicellar region whereas the partial molar volumes of the surfactant in the micellar phase were obtained from data in the postmicellar region. The partial molar expansibility and compressibility were evaluated from the dependence of the partial molar volume on temperature and pressure, respectively. Attention was focused to the expansibility and its pressure coefficient …
Demixing of Mixed Micelles. Thermodynamics of Sodium Perfluorooctanoate−Sodium Dodecanoate Mixtures in Water
1997
Conductivity, density, heat capacity, enthalpy of dilution, and osmotic coefficient measurements of water−sodium perfluorooctanoate (NaPFO)−sodium dodecanoate systems were carried out as functions of the surfactants' total molality (mt) at different mole fractions (XNaPFO). From conductivity data, the critical micelle concentration (cmc) and the degree of ionization (β) of the micelles were derived. The cmc's of the micelles are higher than those of the pure surfactants while β depends linearly on XNaPFO. At a given mole fraction, the apparent molar volume (VΦ) and heat capacity (CΦ) of the mixture increases and decreases monotonically with mt, respectively. From data in the premicellar reg…
Aqueous Laponite Clay Dispersions in the Presence of Poly(ethylene oxide) or Poly(propylene oxide) Oligomers and their Triblock Copolymers
2008
The effect of polyethylene oxide (PEO) or polypropylene oxide (PPO) oligomers of various molecular weight (Mw) as well as of triblock copolymers, based on PEO and PPO blocks, on aqueous laponite RD suspensions was studied with small-angle neutron scattering (SANS). The radius of gyration (RG) increases for low Mw whereas the opposite occurs for larger Mw. This behavior is explained on the-basis that an effective RG is given by two contributions: (1) the size of the particles coated with the polymer and (2) the interactions between the laponite RD particles which are attractive for small and repulsive for large polymers. The SANS curves in the whole Q-range are well described by a model of n…
Characterization of the Cyclodextrin−Surfactant Interactions by Volume and Enthalpy
2003
Volume and enthalpy of transfer of hydroxypropyl-α-cyclodextrin (HP-α-CD) and hydroxypropyl-γ-cyclodextrin (HP-γ-CD) from water to the aqueous solutions of sodium alkanoates (sodium hexanoate, sodium decanoate and sodium dodecanoate) were determined at 298 K. The cyclodextrin concentration was kept constant, and that of the surfactant was varied in order to analyze both the pre- and postmicellar regions. The experimental data in the premicellar region were consistent with the formation of 1:1 and 1:2 (1 cyclodextrin:2 surfactants) inclusion complexes, with the exception of the HP-α-CD/sodium dodecanoate system which presented only the 1:1 complexes. The mechanism of the 1:2 complexes format…
Enthalpies of Mixing of Some Primary Hydrogenated and Fluorinated Alcohols and Sodium Dodecanoate Aqueous Solutions
1993
Abstract The enthalpies of transfer from water to the surfactant solutions ΔH(W → W + S) of some hydrogenated and fiuorinated alkanols and of sodium dodecanoate NaL were determined. In the premicellar region the measurements were carried out as functions of both the additive and the surfactant concentrations in order to evaluate the interaction parameters between the additive and the surfactant molecules. It is shown that in this region, pair, triplet, and quadruplet interaction parameters between unlike solute molecules contribute to ΔH(W → W + S). Within the large uncertainty with which these parameters are determined because of the very narrow surfactant and alcohol concentration interva…
Enthalpies of solution and dilution of butanol and pentanol in dodecyltrimethylammonium bromide micellar solutions
1987
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…