The kinetics and thermodynamics of surfactants in solvent sublation

Solvent sublation has been performed on very dilute solutions of one cationic surfactant, hexadecylpyridinium chloride (HPC), and one anionic surfactant, dodecylbenzenesulfonic acid (LBS). Some thermodynamic values were obtained, e.g. molecular areas, A₀, which are 50.0 and 47.7 Ų/molecule, respectively, for HPC and LBS, and free adsorption energies, ΔG°_ads, which are –33.17 and –43.58 kJ mol^–1, respectively, for HPC and LBS. The kinetics were determined for a range of temperatures and gas flow-rates. Although the processes of solvent sublation of the two surfactants obey first-order kinetics, the respective adsorption mechanisms of HPC and LBS in the solvent sublation process were different. The pH and the presence of KCl and ethanol had no effect on the solvent sublation of LBS. The apparent active energy was calculated as 8.11 kJ mol^–1.     

The removal of humic acids from water by solvent sublation

The application of solvent sublation in the removal of humic acids was investigated in the present study. The humic acids (HA) were removed from an aqueous solution by solvent sublation of humic acid-hexadecylpyridium chloride (HPC) complex (sublate) into isopentanol. Several parameters were examined towards the optimization of humic acid removal; the dosage of a surfactant was found to be the major one, controlling the overall efficiency of the progress. The removal rate was somewhat enhanced by higher airflow rate and almost independent of the volume of the organic solvent floating on the top of the aqueous column. The effects of electrolytes (e.g., NaCl), nonhydrophobic organics (e.g., ethanol), and pH of the solution upon the process were studied. Under the optimized condition, the treatment performance was found to be very efficient, reaching almost 100%, indicating that solvent sublation can serve as a possible alternative technology for the removal of humic acids. The solvent sublation process follows first-order kinetics. A characteristic parameter, apparent activation energy of attachment of the sublate to bubbles, was estimated at a value of 9.48 kJ/mol. Furthermore, the simulation of a mathematical model with the experiments on the solvent sublation of humic acid-HPC was described here.     

溶剂气浮法去除水中的刚果红的研究

以十六烷基三甲基溴化铵为表面活性剂, 与阴离子型染料刚果红形成缔合物, 对该缔合物的溶剂气浮过程进行研究. 研究多种参数对溶剂气浮过程的影响, 如气浮速率、共存溶质的量、pH等参数对溶剂气浮去除率的影响. 研究表明表面活性剂与染料的物质的量之比为2∶1, 约24 min水中刚果红的去除率可达97%;NaCl会大大降低溶剂气浮的去除率;溶剂气浮的速率随着气流速率的增加而增加, 但高速率反而降低溶剂的去除率;共存溶质乙醇存在会使去溶剂去除率降低, 有机溶剂的量对溶剂气浮影响较小;pH中性去除率最佳;考察了不同温度下溶剂气浮的热力学及动力学, 研究表明, 溶剂气浮过程遵从一级动力学, 计算了该过程中的气浮表观活化能为7.48 kJ/mol.     

十六烷基氯化吡啶溶剂气浮的热力学及动力学研究

研究了表面活性剂十六烷基氯化吡啶(HPC)的溶剂气浮回收动力学及热力学规律。通过测定不同温度及浓度下HPC的表面张力, 得到了HPC在气-液界面的标准吸附表面自由能为-33.17 kJ/mol。HPC的溶剂气浮过程符合一级动力学方程,表观速率常数k的值随气体流速升高而增加,随温度升高而降低。     

Studies on the mechanism of Indigo Carmine removal by solvent sublation

Indigo Carmine (C16H8N2Na2O8S2), an anionic dye, was removed from aqueous solution by solvent sublation of Indigo Carmine-cetyltrimethylammonium bromide (CTAB) complex (sublate) into 2-octanol. A stoichiometric amount of surfactant (surfactant:dye=2:1) was demonstrated to be able to remove over 93% IC from the aqueous solution in 5 min. The apparent activation energy of attachment of the sublate to bubbles was calculated as 1.3 kJ/mol. Parameters were considered. At the same time, on the base of the complete transport mechanism, a mathematical model for the dye-surfactant complexation was obtained. Furthermore, the simulation of the mathematical and experimental data was made with good results.     

Study of a mathematical model of metal ion complexes in solvent sublation

Separation of metal ion complex, [(C(12)H(8)N(2))(3)Fe(2+)], with surfactant sodium dodecylphrate (DLS) complex from aqueous phase was carried out by solvent sublation, which obeys first-order kinetics. On the base of the complete transport mechanisms, the Langmuir adsorption, and the ion complex equilibrium in the aqueous phase, a mathematical model for the [(C(12)H(8)N(2))(3)Fe(2+)]-surfactant ion complex is obtained with the aid of the Mathematic 4.0 program, 4th Runge-Kutta method, and the Matlab programs. The effects of many parameters, such as K(a), K(l), K(ow), d(i), V(o), V(w), and Q(a), on solvent sublation are investigated. Furthermore, the simulation showed that the model is substantiated for experiments on the solvent sublation of the complex.     

Adsorption dynamics of binary mixture of Gemini surfactant and opposite-charged conventional surfactant in aqueous solution

The maximum bubble pressure technique has been used to study the adsorption kinetics of binary mixtures of an anionic Gemini surfactant C9pPHCNa with a cationic conventional surfactant C10TABr in aqueous solutions. The dynamic surface tension data were analyzed using the revised Ward and Tordai equations as well as the micelle dissociation kinetic model suggested by Joos et al. The apparent diffusion coefficient Da below the cmc, the adsorption barrier epsilona and the micelle dissociation constant kmic were obtained. The Da s at short times and at long times were respectively 0.2-16 x 10(10) and 0.08-0.9 x 10(10) m2s(-1), the latter corresponded to the adsorption barrier epsilona of 10-20 kJ mol(-1). The minimum epsilona appeared at the mole fraction of C9pPHCNa (alpha1, on a surfactant-only basis) in the bulk solution being 0.33. The kmic s of the mixed micelles were about 16-2300 s(-1). The most stable mixed micelles were formed at alpha1=0.2 rather than at alpha1=0.33 owing to great discrepancy of hydrophobicity between the two components. These results indicated that the composition of mixed solution was an important factor affecting the adsorption kinetics and the micelle stability.     

溶剂气浮法分离水中的Zn离子的研究

以双硫腙为配体,溴化十六烷基三甲基铵（CTAB）为表面活性剂。对Zn离子在无机相中形成的Zn-双硫腙-CTAB体系的溶剂气浮进行了研究。研究表明表面活性剂与Zn离子的物质的量之比为5：1,约1h水中的锌离子去除率可达98％。0．5mol／L NaCl大大提高体系的溶剂气浮的去除率,溶剂气浮的速率随着气流速率的增加而增加,共存溶质乙醇存在会使去除率降低,有机溶剂的量对溶剂气浮影响较小,溶剂气浮过程遵从假一级动力学。考察了不同温度下溶剂气浮的回收速率,计算了该过程中的气浮表观活化能为9．037kJ／mol。     

A mathematical model and mechanism of sublation of dye-surfactant ion complexes

A study of dye-surfactant ion complexes, bromophenol blue (BB), an anionic dye, with hexadecyl pyridium chloride (HPC) complex, and methane violet (MV), a cationic dye, with sodium docedylbenzensulfonate complex (DBS), was carried out. On the base of the complete transport mechanisms, the Langmuir adsorption and the ion complex equilibrium in aqueous phase, a mathematic model for the ion complex system is obtained with the aid of the 4th Runge-Kuta method and the Mathematic 4.0 and Matlab programs. The effects of many parameters are investigated. A substantial difference is posed between the solvent sublation and solvent extraction. Furthermore, the simulation shows that the model is substantiated with experiments on the solvent sublation of the two kinds of complexes. The results are very different from the models proposed by Wilson et al., which predict very different experimental results.     

苯与铂化学吸附作用及其溶剂效应的量子化学研究

The chemical adsorption of Benzene on Pt under the effect of water has been full optimally computed with density functional B3LYP/LanL2DZ from Gaussian 98(A.9 version). The result showed the adsorption of benzene on Pt is a spontaneous process. The adsorption energies are -149.6535 and -202.1635 kJ/mol respectively in two cases, without water and in water. The adsorption energy is decreased in water solvent and the effect of water solvent is shown. The transition state of the transfer Pt on benzene was found by QST2 computation, and corresponding transfer active energies are 61.2537 and 70.8356 kJ/mol without water and in water respectively.     

ADSORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR INDIUM

The adsorption kinetics and mechanism of a nrovel chelate resin, macroporous phosphonic acid resin (PAR) for In(Ill) were investigated Tile statically saturated adsorption capacity is 216mg·g^-1resin at 298K in HAc-NaAc medium. Tire apparent adsorption rate constant is k298=4.84×10^-5 s^-1. Tile adsorption behavior of PAR for In(Ill) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change △H, free energy change △G and entropychange △S of PAR for In(Ⅲ) are 11.5kmol, -12.6kJmol and 80.8Jmol.K, respectively. The apparent activation energy is Ea=3.5k.l/mol. Tire molar coordination ratio of the functional group of PAR to In(Ⅲ) is about 3:1.     

Methylthiolate on Au(111): adsorption and desorption kinetics

Low energy electron diffraction, Auger electron spectroscopy, X-ray photoelectron spectroscopy and line of sight mass spectrometry have been used to study the adsorption and desorption of dimethyldisulfide (DMDS) on Au(111). At 300 K adsorption is dissociative, forming a chemisorbed adlayer of methylthiolate with a 1/3 ML, (sq rt 3 x sq rt 3)R30 degrees, structure. At 100 K adsorption is molecular, with dissociation to form the 1/3 ML (sq rt 3 x sq rt 3)R30 degrees methylthiolate structure occurring at 138-160 K. A physisorbed DMDS layer, with a coverage of 1/6 ML of DMDS, forms on top of the (sq rt 3 x sq rt 3)R30 degrees chemisorbed MT surface for T < or = 180 K, with multilayers forming for T < or = 150 K. In temperature programmed desorption, multilayers of DMDS desorbed with zero order kinetics and an activation energy of 41 kJ mol(-1); the physisorbed layer desorbed with first order kinetics, exhibiting repulsive lateral interactions with an activation energy which varied from 63 kJ mol(-1) (theta = 0) to 51 kJ mol(-1) (theta = 1); the chemisorbed methylthiolate layer desorbed associatively as DMDS via the physisorbed layer, the activation energy for the reaction, 2 methylthiolate --> physisorbed DMDS, exhibiting repulsive lateral interactions with an activation energy which varied from 65 kJ mol(-1) (theta = 0) to 61 kJ mol(-1) (theta = 1). The physisorbed disulfide layer explains the pre-cursor state adsorption kinetics observed in sticking probability measurement, while its relatively facile formation provides a mechanism by which thiolate self-assembled monolayers can become mobile at room temperature.     

Characterization and adsorption properties of tetrabutylammonium montmorillonite (TBAM) clay: thermodynamic and kinetic calculations

The montmorillonite has been subjected to modification through ion-exchange reaction by tetrabutylammonium bromide (TBAB). The modified sample was studied by X-ray diffraction (XRD) technique, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA) methods. The basal spacing of modified montmorillonite was determined as 14.40 A. The IR spectra of modified montmorillonite showed CH vibrations. The characterization of tetrabutylammonium montmorillonite (TBAM) and the adsorption of p-chlorophenol (p-CP) on organomontmorillonite was studied as a function of the solution concentration and temperature. The observed adsorption rates were found to fit to the pseudo-second-order kinetics. The rate constants were calculated for temperatures ranging between 25.0-35.0 degrees C at constant concentration. The adsorption energy, E, and adsorption capacity, (q(m)), for phenolic compounds adsorbing on organomontmorillonite were estimated using the Dubinin-Radushkevich (D-R) equation. Thermodynamic parameters (delta g(a) = -11.063 and -11.802 kJ/mol, delta h(a) = -30.032 and -30.789 kJ/mol, delta s(a) = -0.0636 and -0.0637 kJ/mol K for 298 and 308 K, respectively) were calculated by a new approximation from the adsorption isotherms of p-CP on organomontmorillonite. These isotherms were modeled according to Freundlich and Dubinin-Radushkevich adsorption isotherms, through which the first-order and second-order coefficients (K(1ads) = 0.0152 and 0.0127 micromol/g min, K(2ads) = 0.0130 and 0.0108 L/min micromol, respectively) were obtained at 298 and 308 K.     

Effect of preferential adsorption on the synergism of a homologous cationic surfactant mixture

To evaluate the effect of preferential surface adsorption of bromide ions on the synergism of homologous cationic surfactant mixtures reported previously, the surface tension of the aqueous solutions of the hexadecyltrimethylammonium chloride (HTAC)-dodecyltrimethylammonium bromide (DTAB) system was measured as a function of the total molality of surfactants and the relative proportion of DTAB at 298.15 +/- 0.05 K under atmospheric pressure. The excess Gibbs energies calculated from them were -2.6 kJ mol(-)(1) in the mixed adsorbed film and -2.0 kJ mol(-)(1) in the mixed micelle, respectively. A useful analytical procedure to evaluate the composition of individual ions (hexadecyltrimethylammonium, dodecyltrimethylammonium, chloride, and bromide ions) in the adsorbed film and micelle was developed and applied.     

Surface interactions and quantum kinetic molecular sieving for H2 and D2 adsorption on a mixed metal-organic framework material

A rational strategy has been used to immobilize open metal sites in ultramicroporosity for stronger binding of multiple H 2 molecules per unsaturated metal site for H 2 storage applications. The synthesis and structure of a mixed zinc/copper metal-organic framework material Zn 3(BDC) 3[Cu(Pyen)] .(DMF) 5(H 2O) 5 (H 2BDC = 1,4 benzenedicarboxylic acid and PyenH 2 = 5-methyl-4-oxo-1,4-dihydro-pyridine-3-carbaldehyde) is reported. Desolvation provides a bimodal porous structure Zn 3(BDC) 3[Cu(Pyen)] (M'MOF 1) with narrow porosity (<0.56 nm) and an array of pores in the bc crystallographic plane where the adsorbate-adsorbent interactions are maximized by both the presence of open copper centers and overlap of the potential energy fields from pore walls. The H 2 and D 2 adsorption isotherms for M'MOF 1 at 77.3 and 87.3 K were reversible with virtually no hysteresis. Methods for determination of the isosteric enthalpies of H 2 and D 2 adsorption were compared. A virial model gave the best agreement (average deviation <1 standard deviation) with the isotherm data. This was used in conjunction with the van't Hoff isochore giving isosteric enthalpies at zero surface coverage of 12.29 +/- 0.53 and 12.44 +/- 0.50 kJ mol (-1) for H 2 and D 2 adsorption, respectively. This is the highest value so far observed for hydrogen adsorption on a porous material. The enthalpy of adsorption, decreases with increasing amount adsorbed to 9.5 kJ mol (-1) at approximately 1.9 mmol g (-1) (2 H 2 or D 2 molecules per Cu corresponding to adsorption on both sides of planar Cu open centers) and is virtually unchanged in the range 1.9-3.6 mmol g (-1). Virial analysis of isotherms at 87.3 K is also consistent with two H 2 or D 2 molecules being bound to each open Cu center. The adsorption kinetics follow a double exponential model, corresponding to diffusion along two types of pores, a slow component with high activation energy (13.35 +/- 0.59 kJ mol (-1)) for the narrow pores and a faster component with low activation energy (8.56 +/- 0.41 kJ mol (-1)). The D 2 adsorption kinetic constants for both components were significantly faster than the corresponding H 2 kinetics for specific pressure increments and had slightly lower activation energies than the corresponding values for H 2 adsorption. The kD 2/ kH 2 ratio for the slow component was 1.62 +/- 0.07, while the fast component was 1.38 +/- 0.04 at 77.3 K, and the corresponding ratios were smaller at 87.3 K. These observations of kinetic isotope quantum molecular sieving in porous materials are due to the larger zero-point energy for the lighter H 2, resulting in slower adsorption kinetics compared with the heavier D 2. The results show that a combination of open metal centers and confinement in ultramicroporosity leads to a high enthalpy for H 2 adsorption over a wide range of surface coverage and quantum effects influence diffusion of H 2 and D 2 in pores in M'MOF 1.     

Thermodynamics of naphthalene sorption to organoclays: role of surfactant packing density

Temperature dependence of naphthalene sorption to four organoclays with different surfactant (CTMA+) packing densities was examined. The results showed that both DeltaH o and DeltaS o increase generally with CTMA+ packing density. For organoclays with a low CTMA(+) packing density, the sorption process is driven by both the enthalpy term (DeltaH(o)) and the entropy term (-T DeltaS o), with values ranging from -4.7 to -7.5 kJ mol(-1) and -15.9 to -20.8 kJ mol(-1), respectively. As the CTMA+ packing density increases, the sorption process is driven by the entropy term (from -29.2 to -65.0 kJ mol(-1)) while it is opposed by the enthalpy term (from 7.9 to 40.5 kJ mol(-1)). These results indicate that the enthalpy demand for cavity formation within the surfactant aggregates and the mixing entropy of solute with surfactant aggregates both increase with the surfactant packing density. This means that the surfactant aggregates will form various organic phases as their packing density varies. Controlling the surfactant aggregates within an intermediate packing density range can improve the sorption capacities of the organoclays.     

Hydrogen adsorption in dehydrated variants of the cyano-bridged framework compounds A2Zn3[Fe(CN)6]2.xH2O (A = H, Li, Na, K, Rb)

The impact of coordinatively-unsaturated alkali-metal ions on hydrogen adsorption is studied in dehydrated variants of the compounds A(2)Zn(3)[Fe(CN)(6)](2).xH(2)O (A = H, Li, Na, K, Rb), revealing maximum adsorption enthalpies that vary from 7.7 kJ mol(-1) for A = Na to 9.0 kJ mol(-1) for A = K.     

Estimation of kinetics parameters for the adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes by piezoelectric quartz crystal impedance analysis.

The adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes has been in situ investigated by utilizing the piezoelectric quartz crystal impedance technique. The changes of equivalent circuit parameters were used to interpret the adsorption process. A kinetic model of two consecutive steps was derived to describe the process and compared with a first-order kinetic model by using residual analysis. The experimental data of frequency shift fitted to the model and kinetics parameters, k1, k2, psi1, psi2 and qr, were obtained. All fitted results were in reasonable agreement with the corresponding experimental results. Two adsorption constants (7.19 kJ mol(-1) and 22.89 kJ mol(-1)) were calculated according to the Arrhenius formula.     

Impedance analysis of an electrode-separated piezoelectric sensor as a surface monitoring technique for surfactant adsorption on quartz surface

This paper describes the measurement of the kinetics of adsorption of sodium dodecyl sulfate (SDS), an anionic surfactant, onto a quartz surface with a pre-adsorbed layer of Ca2+ as an ion bridge, using an electrode-separated piezoelectric sensor (ESPS). An impedance analysis method was employed to characterize the responses of the ESPS. The impedance and frequency parameters of the ESPS were examined as functions of the conductivity, permittivity, viscosity and density of the liquid. The adsorption process of SDS onto the quartz surface resulted in an increase in both the mass and energy dissipation of the oscillating quartz crystal. The adsorption densities could be estimated by the ESPS method after taking into consideration the effects of surface viscosity and roughness. The adsorption and desorption rate constants of SDS onto the quartz surface were calculated as ka = (88.1 +/- 0.26) mol(-1) L s(-1) and kd = (4.92 +/- 0.53) x 10(-3) s(-1), respectively, based on the Langmuir model. ESPS was shown to be a powerful means of examining anionic surfactant adsorption to the solid/liquid interface.     

Substituent effects on the adsorption of dialkyl sulfides on gold nanoparticles

The adsorption of chloroethyl ethyl sulfide and 2,2'-dichloro ethyl sulfide to gold nanoparticles has been examined in the gas phase using surface-plasmon resonance spectroscopy. The equilibrium constants for the gas-phase adsorption reactions are 14 +/- 4 and 25 +/- 5 atm(-1), respectively. The bond energy of the Au-chloroethyl ethyl sulfide complex is 44 +/- 9 kJ mol(-1). The bond energy of Au-2,2'-dichloro ethyl sulfide is estimated to be 47 kJ mol(-1). Halogenation of the dialkyl side chains is found to have little impact on the chemistry, and only physisorption processes occur, analogous to dialkyl sulfide adsorption on Au surfaces.