Exploration of the fundamental equilibrium behaviour of calcium exchange with weak acid cation resins

This study evaluated the complexity of calcium ion exchange with sodium exchanged weak acid cation resin (DOW MAC-3). Exchange equilibria recorded for a range of different solution normalities revealed profiles which were represented by conventional “L” or “H” type isotherms at low values of equilibrium concentration (Ce) of calcium ions, plus a superimposed region of increasing calcium uptake was observed at high Ce values. The loading of calcium ions was determined to be ca. 53.5 to 58.7 g/kg of resin when modelling only the sorption curve created at low Ce values,which exhibited a well-defined plateau. The calculated calcium ion loading capacity for DOWMAC-3 resin appeared to correlate with the manufacturer's recommendation. The phenomenon of super equivalent ion exchange (SEIX) was observed when the “driving force” for the exchange process was increased in excess of 2.25 mmol calcium ions per gram of resin in the starting solution. This latter event was explained in terms of displacement of sodium ions from sodium hydroxide solution which remained in the resin bead following the initial conversion of the as supplied “H+” exchanged resin sites to the “Na+” version required for softening studies. Evidence for hydrolysis of a small fraction of the sites on the sodium exchanged resin surface was noted. The importance of carefully choosing experimental parameters was discussed especially in relation to application of the Langmuir–Vageler expression. This latter model which compared the ratio of the initial calcium ion concentration in solution to resin mass, versus final equilibrium loading of the calcium ions on the resin; was discovered to be an excellent means of identifying the progress of the calcium–sodium ion exchange process. Moreover, the Langmuir–Vageler model facilitated standardization of various calcium–sodium ion exchange experiments which allowed systematic experimental design.

Equilibrium and column studies of iron exchange with strong acid cation resin

The exchange of iron species from iron (III) chloride solutions with a strong acid cation resin has been investigated in relation to a variety of water and wastewater applications. A detailed equilibrium isotherm analysis was conducted wherein models such as Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov, Sips and Brouers-Sotolongo were applied to the experimental data. An important conclusion was that both the bottle-point method and solution normality used to generate the ion exchange equilibrium information influenced which sorption model fitted the isotherm profiles optimally. Invariably, the calculated value for the maximum loading of iron on strong acid cation resin was substantially higher than the value of 47.1 g/kg of resin which would occur if one Fe3+ ion exchanged for three “H+” sites on the resin surface. Consequently, it was suggested that above pH 1, various iron complexes sorbed to the resin in a manner which required less than 3 sites per iron moiety. Column trials suggested that the iron loading was 86.6 g/kg of resin when 1342 mg/L Fe (III) ions in water were flowed at 31.7 bed volumes per hour. Regeneration with 5 to 10 % HCl solutions reclaimed approximately 90 % of exchange sites.

Rate capability of graphite materials as negative electrodes in lithium-ion capacitors

The lithium-ion exchange rate capability of various commercial graphite materials are evaluated using galvanostatic charge/discharge cycling in a half-cell configuration over a wide range of C-rates (0.1 similar to 60C). The results confirm that graphite is capable of de-intercalating stored charge at high rates, but has a poor intercalating rate capability. Decreasing the graphite coating thickness leads to a limited rate performance improvement of the electrode. Reducing the graphite particle size shows enhanced C-rate capability but with increased irreversible capacity loss (ICL). It is demonstrated that the rate of intercalation of lithium-ions into the graphite is significantly limited compared with the corresponding rate of de-intercalation at high C-rates. For the successful utilisation of commercially available conventional graphite as a negative electrode in a lithium-ion capacitor (LIC), its intercalation rate capability needs to be improved or oversized to accommodate high charge rates.

Equilibrium studies of ammonium exchange with Australian natural zeolites

This paper is concerned with the study of the equilibrium exchange of ammonium ions with two natural zeolite samples sourced in Australia from Castle Mountain Zeolites and Zeolite Australia. A range of sorption models including Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov and Brouers–Sotolongo were applied in order to gain an insight as to the exchange process. In contrast to most previous studies, non-linear regression was used in all instances to determine the best fit of the experimental data. Castle Mountain natural zeolite was found to exhibit higher ammonium capacity than Zeolite Australia material when in the freshly received state, and this behavior was related to the greater amount of sodium ions present relative to calcium ions on the zeolite exchange sites. The zeolite capacity for ammonium ions was also found to be dependent on the solution normality, with 35–60% increase inuptake noted when increasing the ammonium concentration from 250 to 1000 mg/L. The optimal fit ofthe equilibrium data was achieved by the Freundlich expression as confirmed by use of Akaikes Information Criteria. It was emphasized that the bottle-point method chosen influenced the isotherm profile in several ways, and could lead to misleading interpretation of experiments, especially if the constant zeolite mass approach was followed. Pre-treatment of natural zeolite with acid and subsequently sodium hydroxide promoted the uptake of ammonium species by at least 90%. This paper highlighted the factors which should be taken into account when investigating ammonium ion exchange with natural zeolites.

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Characterization of Er3+-doped Na2O-WO3-TeO2 glass for ion-exchanged waveguide amplifiers and lasers

Er^(3+)-doped Na2O-WO3-TeO2 glass consistent with standard ion-exchange technology has been fabricated and characterized. The measured absorption and emission spectra of the glass were analyzed by the Judd-Ofelt and McCumber theories. The intensity parameters are Ω2 = 7.01

Analysis of steric mass-action model for protein adsorption equilibrium onto porous anion-exchange adsorbent

The ion-exchange equilibrium of bovine serum albumin (BSA) to an anion exchanger, DEAE Spherodex M, has been studied by batch adsorption experiments at pH values ranging from 5.26 to 7.6 and ionic strengths from 10 to 117.1 mmol/l. Using the unadjustable adsorption equilibrium parameters obtained from batch experiments, the applicability of the steric mass-action (SMA) model was analyzed for describing protein ion-exchange equilibrium in different buffer systems. The parametric sensitivity analysis was performed by perturbing each of the model parameters, while holding the rest constant. The simulation results showed that, at high salt concentrations or low pHs close to the isoelectric point of the protein, the precision of the model prediction decreased. Parametric sensitivity analysis showed that the characteristic charge and protein steric factor had the largest effects on ion-exchange equilibrium, while the effect of equilibrium constant was about 70%-95% smaller than those of characteristic charge and steric factor under all conditions investigated. The SMA model with the relationship between the adjusted characteristic charge and the salt concentration can well predict the protein adsorption isotherms in a wide pH range from 5.84 to 7.6. It is considered that the SMA model could be further improved by taking into account the effect of salt concentration on the intermolecular interactions of proteins. (c) 2006 Elsevier Ltd. All rights reserved.

Capillary electrochromatographic separation of ionizable compounds with a molecular imprinted monolithic cationic exchange column

A polymer-based monolithic capillary column imprinted with 4-aminopyridine (4-AP) was prepared by a thermally-initiated polymerization process; and its performance as a capillary electrochromatographic medium was evaluated in separating 4-AP and 2-AP isomers. The effects of experimental parameters, such as pH value and ionic strength of the buffer, the acetonitrile content in the mobile phase, and the applied voltage, on the resolution of these isomers had been carefully investigated. It was found that in the retention process there were interplays of multiple mechanisms of ion-exchange, molecular imprinting, and electrophoresis. These mechanisms allowed more sophisticated control of experimental parameters in the separation of ionizable compounds.

Sulfonated poly(ether ether ketone)/clay-SO3H hybrid proton exchange membranes for direct methanol fuel cells Journal of Power Sources

A new type of sulfonated clay (clay-SO3H) was prepared by the ion exchange method with the sulfanilic acid as the surfactant agent. The grafted amount of sulfanilic acid in clay-SO3H was 51.8 mequiv. (100 g)(-1), which was measured by thermogravimetric analysis (TGA). Sulfonated poly(ether ether ketone) (SPEEK)/clay-SO3H hybrid membranes which composed of SPEEK and different weight contents of clay-SO3H, were prepared by a solution casting and evaporation method. For comparison, the SPEEK/clay hybrid membranes were produced with the same method.

Synthesis of sulfonated poly(arylene-co-naphthalimide)s as novel polymers for proton exchange membranes

A series of novel sulfonated poly(arylene-co-binaphthalimide)s (SPPIs) were successfully synthesized via Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and bis(chloronaphthalimide)s. Bis(chloronaphthalimide)s were conveniently prepared from 5-chloro-1,8-naphthalic anhydride and various diamines. Tough and transparent SPPI membranes were prepared and the electrolyte properties of the copolymers were intensively investigated as were the effects of different diamine structures on the copolymer characterisitics. The copolymer membrane Ia-80, with an ion exchange capacity (IEC) of 2.50 meq g(-1), displayed a higher proton conductivity, i.e. 0.135 S cm(-1) at 20 degrees C, as compared to Nafion 117 (0.09 S cm(-1), 20 degrees C).

Tunable wettability by counterion exchange at the surface of electrostatic self-assembled multilayers

A novel method to tune surface wettability rapidly and reversibly has been developed by ion exchange of the counterions at the surface of a multilayer film assembled via electrostatic interaction.

Ion-Responsive Behavior of Ionic-Liquid Surfactant Aggregates with Applications in Controlled Release and Emulsification

We propose a simple but efficient, rapid, and quantitative ion-responsive micelle system based on counter-anion exchange of a surfactant with an imidazolium unit. The ion-exchange reaction results in the amphiphilic-to-hydrophobic transition of the imidazolium salt, leading to the destruction of the micelles, which has been successfully applied to control led release and emulsification.

Incorporation of Nanoparticles into Polyelectrolyte Multilayers via Counterion Exchange and in situ Reduction

We report a general method for incorporation of nanoparticles into polyelectrolyte multilayer (PEM) thin films by utilizing the excess charges and associated counterions present in the PEMs. Silver ions were introduced directly into multilayers assembled from poly(diallyldimethylammonium chloride) (PDDA) and poly(styrene sulfonate) (PSS), (PDDA/PSS)(n), by a rapid ion exchange process, which were then converted into silver nanoparticles via in situ reduction to create composite thin films. The size and the content of the nanoparticles in the film call be tuned by adjusting the ionic strength in the polyelectrolyte solutions used for the assembly. Spatial control over the distribution of the nanoparticles in the PEM was achieved via the use of multilayer heterostructure containing PDDA/PSS bilayer blocks assembled at different salt concentrations. Because excess charges and counterions are always present in any PEM, this approach can be applied to fabricate a wide variety of composite thin Films based on electrostatic self-assembly.

Counterion exchange at the surface of polyelectrolyte multilayer film for wettability modulation

Counterions present at the surface of polyelectrolyte multilayers (PEMs) were utilized for modulation of surface wettability via ion exchange. The PEM film was dipped in aqueous solutions of different anions, respectively, and the water contact angle of the surface varied from about 10 degrees to 120 degrees, depending on the hydration characteristics of the anion. The ion exchange mechanism was verified by X-ray photoelectron spectroscopy. The process was rapid and reversible. Ionic strength of the polyelectrolyte solution used for preparing the PEMs was found to be crucial to the surface wetting properties and the reversibility and kinetics of the process, and the effects were correlated to the surface density of the excess charge and counterion. This work provides a general, facile and rapid approach of surface property modulation.

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.