Ion-Exchange Kinetics

A novel study on the speciation of aluminum in solution has been reported by Bertsch et al. [35], Fluoro, oxalato, and citrate aluminum complexes were identified as distinct peaks together with free AI(IIl). Post-column reaction/UV detection was used. These studies were used in kinetic, ion-exchange, and toxicological investigations. 

Helfferich, F., Ion-exchange kinetics, ion exchange-a series of advances, Vol. 1, Marcel Dekker, New York, 1966, p. 65. 

Post-synthesis modification comes into its own when preparing molecular sieves with desirable and exploitable properties other than those of ion exchange, be they optical, magnetic, catalytic or adsorptive. Here it is not directly the thermodynamic and kinetic ion exchange properties that are of prime importance but rather which experimental, preparative methods are most commonly used. Thus it is important to assess what are the most appropriate experimental methods of preparation, as well as to review the many pitfalls one can fall into which can subsequently give rise to very inaccurate and inadequate experimental data. These experimental problems can include framework hydrolysis, hydronium exchange, dealvunination, the presence of key trace impurities, ssolution phenomena, carbonate and bicarbonate interference, colloidal phenomena, metal ion complex formation and cation hydrolysis. 

Both the kinetics and the equilibrium aspects of ion exchange involve more than purely surface chemical considerations. Thus, the formal expression for the exchange... 

Divinylbenzene copolymers with styrene are produced extensively as supports for the active sites of ion-exchange resins and in biochemical synthesis. About 1—10 wt % divinylbenzene is used, depending on the required rigidity of the cross-linked gel, and the polymerization is carried out as a suspension of the monomer-phase droplets in water, usually as a batch process. Several studies have been reported on the reaction kinetics (200,201). 

A. S. Michaels Simplified Method of Interpreting Kinetic Data in Fixed-Bed Ion Exchange, Industrial and Engineering Chemistry, 44(8) 1922 (1952). 

Purely parallel reactions are e.g. competitive reactions which are frequently carried out purposefully, with the aim of estimating relative reactivities of reactants these will be discussed elsewhere (Section IV.E). Several kinetic studies have been made of noncompetitive parallel reactions. The examples may be parallel formation of benzene and methylcyclo-pentane by simultaneous dehydrogenation and isomerization of cyclohexane on rhenium-paladium or on platinum catalysts on suitable supports (88, 89), parallel formation of mesityl oxide, acetone, and phorone from diacetone alcohol on an acidic ion exchanger (41), disproportionation of amines on alumina, accompanied by olefin-forming elimination (20), dehydrogenation of butane coupled with hydrogenation of ethylene or propylene on a chromia-alumina catalyst (24), or parallel formation of ethyl-, methylethyl-, and vinylethylbenzene from diethylbenzene on faujasite (89a). 

Anderson and Bonner made the first detailed kinetic study on the exchange using the isotopic method ( Cr) and a separation method based on the conversion of Cr(II) into Cr(IIl) oxalate and an ion-exchange treatment. To prevent oxidation of Cr(II) during exchange a hydrogen atmosphere was maintained over the reaction mixture. The rate law found to be obeyed for the concentration ratio range Cr(III)/Cr(II) of between 3.3 x 10 and 2.0 in perchlorate media was... 

Catalysts include oxides, mixed oxides (perovskites) and zeolites [3]. The latter, transition metal ion-exchanged systems, have been shown to exhibit high activities for the decomposition reaction [4-9]. Most studies deal with Fe-zeolites [5-8,10,11], but also Co- and Cu-systems exhibit high activities [4,5]. Especially ZSM-5 catalysts are quite active [3]. Detailed kinetic studies, and those accounting for the influence of other components that may be present, like O2, H2O, NO and SO2, have hardly been reported. For Fe-zeolites mainly a first order in N2O and a zero order in O2 is reported [7,8], although also a positive influence of O2 has been found [11]. Mechanistic studies mainly concern Fe-systems, too [5,7,8,10]. Generally, the reaction can be described by an oxidation of active sites, followed by a removal of the deposited oxygen, either by N2O itself or by recombination, eqs. (2)-(4). 

During caustic waterflooding the alkali can be consumed by the dissolution of clays and is lost in this way. The amount lost depends on the kinetics of the particular reaction. Several studies have been performed with kaolinite, using quartz as a yardstick, because the kinetic data are documented in the literature. The initial reaction rate has been found pH independent in the pH range of 11 to 13 [517]. The kinetics of silica dissolution could be quantitatively described in terms of pH, salinity, ion-exchange properties, temperature, and contact time [1549]. 

Ion-exchange processes are strictly heterogeneous reactions that involve two phases. They, however, mostly comply with homogeneous, second-order reaction kinetics. An exchange reaction represented by... 

Spirodela intermedia, L. minor, and P. stratiotes were able to remove Pb(II), Cd(II), Ni(II), Cu(II), and Zn(II), although the two former ions were removed more efficiently. Data fitted the Langmuir model only for Ni and Cd, but the Freundlich isotherm for all metals tested. The adsorption capacity values (K ) showed that Pb was the metal more efficiently removed from water solution (166.49 and 447.95 mg/g for S. intermedia and L. minor, respectively). The adsorption process for the three species studied followed first-order kinetics. The mechanism involved in biosorption resulted in an ion-exchange process between monovalent metals as counterions present in the macrophytes biomass and heavy metal ions and protons taken up from water.112... 

Helminen J, Leppamaki M, Paatero E and Minkkinen (1998) Monitoring the Kinetics of the Ion-exchange Resin Catalysed Esterification of Acetic Acid with Ethanol Using Near Infrared Spectroscopy with Partial Least Squares (PLS) Model, Chemometr Intell Lab Syst, 44 341. 

As a model esterification reaction, the formation of ethyl lactate has been studied and its complete kinetic and thermodynamic analysis has been performed. The formation rate of ethyl lactate has been examined as a function of temperature and catalyst loading. In early experiments, it was determined that lactic acid itself catalyzes esterification, so that there is significant conversion even without ion exchange resin present. The Arrhenius plot for both resin-catalyzed and uncatalyzed reactions indicates that the uncatalyzed... 

---