Response of the cation-sensitive glass electrodes to alkyl-substituted ammonium ions

Summary The response of cation-sensitive glass electrodes to alkyl-substituted ammonium ions has been evaluated. Increasing ion size results in decreasing electrode selectivity, progressively greater deviations from the Nernst slope, and increasing equilibration times. Direct potentiometric measurements should be suited to the estimation of smaller alkyl-substituted ammonium ions in the presence of multivalent cations.

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Zusammenfassung In der vorliegenden Untersuchung wurde das Ansprechen von kation-empfindlichen Glaselektroden auf alkylsubstituierte Ammoniumionen geprüft. Mit steigender Größe des Ions konnte eine Abnahme der Selektivität der Elektrode, zunehmende Abweichungen von der Nernstschen Gleichung und eine wachsende Zeitdauer für die Einstellung des Gleichgewichts beobachtet werden. Es ergab sich, daß die kation-empfindliche Glaselektrode zur Bestimmung kleinerer alkylsubstituierter Ammoniumionen in Gegenwart mehrwertiger Kationen verwendet werden kann.

     

Self-assembly of cetyl trimethylammonium bromide in ethanol-water mixtures

The critical micelle concentration (CMC) of cetyl trimethylammonium bromide (CTAB) in both water and ethanol-water-mixed solvent was determined using steady-state fluorescence techniques in order to investigate the effect of the self-assembling properties of the surfactant on the template synthesis of porous inorganic materials. Results indicated that the CMC increased with the increase of ethanol concentration in the mixed solvent. The CMC of CTAB is 0.0009 mol/L in water, while it is 0.24 mol/L in ethanol. Furthermore, the dissipative particle dynamics (DPD) was adopted to simulate the aggregation of CTAB in water and ethanol/water mixtures, and the energy difference was calculated for the surfactant tail groups after mixing with the solvent. The simulation results reflected a regularity similar to the experimental data, i.e., tail groups of CTAB interacted more strongly with ethanol than with groups of CTAB interacted more strongly with ethanol than with water, which elucidates the reason that the micelle is difficult to form in ethanol. __________ Translated from Journal of Tianjin University, 2006, 39(1) (in Chinese)     

On the mutual diffusion properties of ethanol-water mixtures

The structural organization, the number of hydrogen bonds (H bond), and the self- and mutual diffusion coefficients of ethanol-water mixtures were studied by molecular dynamics simulation. It was found that both the numbers of H bonds per water and per ethanol decrease as the mole fraction of ethanol increases. The composition dependences and the relationships between the self- and the mutual diffusion coefficients were further discussed. The self-diffusion coefficient of water has a large drop as the concentration of ethanol increases from 0 to 0.3 and then it nearly keeps constant, while that of ethanol has a minimum around ethanol mole fraction of 0.5. The mutual diffusion coefficient could be divided into two parts, the kinematic factor and the thermodynamic factor. Both the kinematic and thermodynamic factors for ethanol-water mixtures were calculated. It was found that the change trend of mutual diffusion coefficients with the composition is mainly dependent on the thermodynamic factors.     

Potentiometric titration of cyanide using the cation-sensitive glass electrode as indicator

Summary The argentometric determination of cyanide was re-examined in order to compare the cation-sensitive glass electrode and the silver metal electrode as indicator electrodes for this titration. Contrary to earlier reports, the glass electrode is capable of indicating both titration end points and yields stoichiometric information comparable to or better than that obtained with the silver metal electrode. In the presence of redox interferences, the glass electrode is superior to the silver metal electrode for titration purposes.

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Zusammenfassung Die argentometrische Cyanidbestimmung wurde im Hinblick auf einen Vergleich der kation-empfindlichen Glaselektrode und der Silberelektrode als Indicatorelektroden nochmals untersucht. Im Gegensatz zu früheren Berichten ergab sich, daß die Glaselektrode beide Endpunkte der Titration anzeigen kann und Aussagen über die Stöchiometrie gestattet, die vergleichbar oder besser sind als die mit Hilfe der Silberlektrode erhaltenen. In Gegenwart von Oxydations- oder Reduktionsmitteln erweist sich die Glaselektrode als besser geeignet.

     

Activity coefficients for NaCl in ethanol-water mixtures at 25°C

Activity coefficient values for NaCl in ethanol-water mixtures containing 20, 40, 60, 70, 80 and 90 weight % ethanol are calculated from the emf for the galvanic cell $$Na - glass|NaCl(m), H_2 O (100 - Y), EtOH(Y), AgCl|Ag$$ in which the weight % of the corresponding solvent is indicated in parenthesis. The results obtained are analyzed by using different theoretical models. Chemical models which take into account the presence of ion pairs in solutions of high ethanol content are also used. There is good agreement between the results obtained from all the models.     

Evaporation of ethanol and ethanol-water mixtures studied by time-resolved infrared spectroscopy

The knowledge of the physics and the chemistry behind the evaporation of solvents is very important for the development of several technologies, especially in the fabrication of thin films from liquid phase and the organization of nanostructures by evaporation-induced self-assembly. Ethanol, in particular, is one of the most common solvents in sol-gel and evaporation-induced self-assembly processing of thin films, and a detailed understanding of its role during these processes is of fundamental importance. Rapid scan time-resolved infrared spectroscopy has been applied to study in situ the evaporation of ethanol and ethanol-water droplets on a ZnSe substrate. Whereas the evaporation rate of ethanol remains constant during the process, water is adsorbed by the ethanol droplet from the external environment and evaporates in three stages that are characterized by different evaporation rates. The adsorption and evaporation process of water in an ethanol droplet has been observed to follow a complex behavior: due to this reason, it has been analyzed by two-dimensional infrared correlation. Three different components in the water bending band have been resolved.     

Selectivity coefficient changes for liquid-membrane electrodes

The effects of the activity levels of the measured ion and interfering ions, and of the detection limit of the electrode on the values of selectivity coefficients for liquid-membrane ion-selective electrodes are discussed. The coefficients were determined by the mixed-ion solution method. Depending on the activity of the interfering ion, the activity of the main ion for which the selectivity coefficient is determined may differ. The best conditions of measurement are those which involve the largest contribution from the term containing the selectivity coefficient in the Nikolsky equation; the measurements are then most precise, and the values of the selectivity coefficients describe the electrode behaviour most consistently. When the limit of detection of the electrode is comparable with the other terms, it must be taken into account in calculations. Under the optimal conditions, selectivity coefficients were calculated for the Orion calcium and divalent cation electrodes, with calcium as the main ion and alkali metal ions as interfering ions.     

Molecular dynamics study of hydration in ethanol-water mixtures using a polarizable force field

The abnormal physicochemical characteristics of ethanol solvation in water are commonly attributed to the phenomenon of hydrophobic hydration. To investigate the structural organization of hydrophobic hydration in water-ethanol mixtures, we use molecular dynamics simulations based on detailed atomic models. Induced polarization is incorporated into the potential function on the basis of the classical Drude oscillator model. Water-ethanol mixtures are simulated at 11 ethanol molar fractions, from 0.05 to 0.9. Although the water and ethanol models are parametrized separately to reproduce the vaporization enthalpy, static dielectric constant, and self-diffusion constant of neat liquids at ambient conditions, they also reproduce the energetic and dynamical properties of the mixtures accurately. Furthermore, the calculated dielectric constant for the various water-alcohol mixtures is in excellent agreement with experimental data. The simulations provide a detailed structural characterization of the mixtures. A depletion of water-water hydrogen bonding in the first hydration shell of ethanol is compensated by an enhancement in the second hydration shell. The structuring effect from the second solvation shell gives rise to a net positive hydrogen-bonding excess for ethanol molar fractions up to approximately 0.5. For larger molar fractions, the second hydration shell is not sufficiently populated to overcome the net H-bond depletion from the first shell.     

Formation of cobalt, nickel and copper complexes with murexide in ethanol-water mixtures

The complexation reactions between murexide and Co²⁺, Ni²⁺ and Cu²⁺ in C₂H₅OH-H₂O mixtures have been investigated spectrophotometrically. The formation constants of the 1:1 complexes formed increase in the order Co²⁺ < Ni²⁺ < Cu²⁺ for all solvent mixtures studied, and log K_f is a linear function of the mole fraction of ethanol. The heat of complexation was determined calorimetrically for the nickel and copper complexes. The values of ΔH° and ΔS° are solvent-dependent, and all three complexes have negative ΔH° and positive ΔS° values.     

Selectivity enhancement of anion-responsive electrodes by pulsed chronopotentiometry

A large and robust selectivity improvement of ion-selective electrodes is presented for the measurement of abundant ions. An improvement in selectivity by more than two orders of magnitude has been attained for the hydrophilic chloride ions measured in a dilute background of the lipophilic ions perchlorate and salicylate in a pulsed chronopotentiometric measurement mode. This is attributed to a robust kinetic discrimination of the dilute lipophilic ions in this measuring mode, which is not possible to achieve in classical potentiometry. Maximum tolerable concentrations of the interfering ions are found to be on the order of 30 μM before causing substantial changes in potential. As an example of practical relevance, the robust detection of chloride in 72 μM salicylate (reflecting 1:10 diluted blood) with a detection limit of 0.5 mM chloride is demonstrated. Corresponding potentiometric sensors did not give a useful chloride response under these conditions.     

Transference numbers for KCl in ethanol-water and dioxane-water mixtures at 25°C

Transference numbers were determined by the moving-boundary method for KCl in aqueous mixtures containing 12, 20, 40, 60, and 79 wt. % ethanol, and 22, 44, 62, and 75 wt. % 1,4-dioxane. The boundaries were detected by the potentiometric method using an autogenic cell with a cadmium anode. Little concentration dependence was expected since all the transference numbers were close to 0.5. The Fuoss-Onsager theory for the electrophoretic effects was used for extrapolation to infinite dilution. The precision of the measurements appears to be well within 0.05%.These measurements were performed at Brown University, Providence, Rhode Island, and at Mellon Institute, Carnegie-Mellon University, Pittsburgh, Pennsylvania.     

The role of ethanol-water solvent mixtures in N719 sensitization of electrodeposited ZnO nanorods

Water plays an important role in N719 sensitization of ZnO films for application as photoanodes in DSC devices. The role of water content in ethanolic N719 sensitization solutions was examined resorting to N719-solvent interaction studies based on Kamlet-Taft solvatochromic parameters. Results show that as the water content increases, solvent’s HBA ability decreases, hindering dye aggregation in solution and increasing the fraction of dye carboxylic groups available for anchorage onto the charged ZnO surface. The impact of dye-dye-solvent equilibria in solution on ZnO nanorod films sensitization and device behavior was evaluated. Devices assembled with films sensitized in N719 solutions containing equal parts of ethanol and water showed a twofold increase in short-circuit current densities when compared to those sensitized in ethanol only, despite exhibiting significantly less stained films. Data indicate that the presence of water in the sensitization solution reduces the amount of dye aggregates in solution and on the ZnO surface.     

Solvent structure in aqueous mixtures. III. Ionic conductances in ethanol-water mixtures at 10 and 25°C

Viscosities at 10 and 25°C and dielectric constants at 10°C are reported for ethanol-water mixtures. Precise transference numbers for KBr at 10°C were determined by the moving-boundary method for five solvent mixtures containing up to 20 mole % ethanol. Conductance measurements for the alkali halides and tetraalkylammonium bromides were carried out across the complete range of solvent composition at 25°C, but for the water-rich region only at 10°C. The resulting limiting ionic Walden products confirmed the conclusions arrived at from earlier measurements. The maxima occurring in the water-rich region cannot be attributed solely to a structure-breaking effect owing to the ionic size dependence which is in the wrong direction. The tetraalkylammonium ions in these mixtures do not exhibit an enhanced hydrophobic effect, nor do they appear to enhance structure of any kind. Rather, the addition of alcohol to an aqueous Bu₄N⁺ solution merely reduces the magnitude of the hydrophobic effect, as illustrated by a steadily increasing Walden product in the water-rich region. A decrease in temperature has no effect on the Walden product for the Bu₄N⁺ ion but increases the magnitude of the maxima for the alkali-metal and halide ions. These maxima are attributed to sorting of the solvent components by the ionic charge, due to an acid-base type interaction, so that the proportion of water in the ionic cospheres is greater than in the bulk solvents. The sorting effect is shown to be temperature independent. The oxyanions are shown to exhibit a behavior in these mixtures that cannot be identified at this time.     

Kinetics of the periodate oxidation of octacyanomolybdate(IV) in ethanol-water solvent mixtures

The kinetics of the oxidation of Mo(CN) ₈ ^4– by IO ₄ ^– has been studied in ethanol—water solvent mixtures over a temperature range of 15–35 °C. The effect of solvent composition on the reaction rate and the mechanism has been investigated. Activation parameters are given. An inner-sphere mechanism, consistent with the kinetic results, is proposed.

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Kinetik der Periodat-Oxidation von Octacyanomolybdat(IV) in Ethanol-Wasser

Zusammenfassung Die Kinetik der Oxidation von Mo(CN) ₈ ^4– mit IO_4/– wurde in Ethanol—Wasser über einen Temperaturbereich von 15–35 °C untersucht. Der Effekt der Lösungsmittelzusammensetzung auf die Reaktionsgeschwindigkeit und der Mechanismus der Reaktion werden diskutiert. Die Aktivierungsparameter sind angeführt. Es wird ein Inner-Sphere-Mechanismus vorgeschlagen, der mit den kinetischen Ergebnissen konsistent ist.

     

Vapor permeation of ethanol-water mixtures using sodium alginate membranes with crosslinking gradient structure

For the vapor permeation of ethanol-water mixtures, two types of dense sodium alginate (SA) membranes have been prepared: a nascent SA membrane and crosslinked SA membranes with glutaraldehyde (GA). In the vapor permeation of the concentrated ethanol-water mixtures through the SA membranes, the effects of feed temperature, cell temperature and crosslinking density in the membrane were investigated on the membrane performance, and a comparison of vapor permeation process was made with pervaporation. SA membranes having different crosslinking gradients have been fabricated by exposing the nascent membrane to different GA content of reaction solutions. The extent of the gradient was controlled by the exposing time. The permeation performance of the membranes will be discussed with the extent of the gradient. An optimal crosslinking gradient was determined in terms of flux and membrane stability. The separation of ethanol-water mixtures through the membrane with the optimal crosslinking gradient was carried out by vapor permeation and the permeation performance will be discussed, and compared with pervaporation.     

Evaporation of microdroplets of ethanol-water mixtures on gold surfaces modified with self-assembled monolayers

The wetting property and evaporation behavior of ethanol-water mixtures of various concentrations on gold surfaces modified with 1-decanethiolate self-assembled monolayers (SAMs) were studied by digital contact angle analysis. It has been shown that the initial contact angle decreases monotonically with increased concentration of ethanol in the mixture. Evaporation studies revealed a general trend with a preliminary increase in contact angle accompanied with a decrease in contact area, then a constant contact angle accompanied with a slower, linear decrease in contact area. At the very beginning of the evaporation process, the contact angles showed a rapid decrease for the microdroplets of a binary mixture with equal volume fractions (i.e., 50% ethanol). Three distinct stages of the evaporation profile for the ethanol-water mixtures were observed, which differ from the inclusive "pinning" and "shrinking" behavior observed for the pure liquid case. Ultimately, the study makes possible the use of an evaporation profile to monitor the change in concentration of a binary system and allows a better understanding of the interactions between liquid microdroplets with solid substrates.     

Time-dependent selectivity of glass membrane electrodes

Time-dependent selectivities of both sodium- and hydrogen-selective glass membrane electrodes are investigated. Results indicate that these electrodes display little selectivity shortly after an increase or decrease in the activityof another cation at the electrode surface. Selectivity appears to increase as the potential approaches a steady-state value. A physical model is considered which accounts for the time-dependent selectivity with the generation of a chemical potential difference across the interface between the bulk solution and the hydrated glass layer.     

Melting temperature of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water mixtures

The melting temperature (T _m) of colloidal crystals of monodisperse silica spheres in ethanol-water and ethylene glycol-water suspensions has been measured by reflection spectroscopy. A sphere of 110 nm in diameter and 0.041 in monodispersity index is used after purification and deionization processes. Transformation from the body-centered cubic lattice to the face-centered cubic lattice subphases is observed as the suspension temperature rises, which is similar to the purely aqueous suspension of the same sphere. A phase diagram including liquid-like and crystal-like structures is obtained in the presence of ion-exchange resins coexisted. The data ofT _m are analyzed successfully with the theory of Williams, Crandall, and Wojtowicz. The heat of melting decreases by the addition of ethanol or ethylene glycol in the mixtures.