Cationic starch iodophores

Cross‐linked cationic starches N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium starch chloride (CQS chloride), N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium starch iodide (CQS iodide), and N‐(2‐hydroxyl)propyl‐3‐trimethyl ammonium starch iodide–iodine (CQS triiodide) with the degree of substitution (DS) according to cationic groups from 0.04 to 0.62, as well as cross‐linked starch–iodine complexes were synthesized and tested as potential antibacterial agents. Cationic starch iodine derivatives were obtained during ion exchange reaction between CQS chloride and iodide or iodide–iodine anions in aqueous solutions. CQS_DS≤0.3 chloride can form several types of iodine complexes, such as the blue amylose–iodine inclusion complex and ionic CQS⁺I^?·(I₂)_m complex (m ≥ 1). The antibacterial activity of modified starches–iodine samples against different pathogenic bacterial cultures and contaminated water microorganisms was evaluated. CQS chloride and CQS iodide were found to be bacteriostatic. A strong antibacterial activity was characteristic of CQS triiodides in which molecular iodine is present in both ionic and inclusion complexes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

NMR-study of structure and dynamics of associates of syndiotactic poly(methyl methacrylate) in toluene

Summary High-resolution ¹H NMR spectra (¹H HR-NMR) of solutions of isotactic (i) and syndiotactic (s) poly(methyl methacrylate) (PMMA) in toluene-d₈ were measured in the concentration range 0.2 to 10% w/v; for solutions of s-PMMA (10% w/v), ¹H NMR spectra with magic angle rotation (MAR-NMR) at various temperatures and ¹³C NMR spectra with strong proton decoupling were also measured. It was found that even in very dilute solutions of s-PMMA in toluene-d₈ a considerable portion (76%) of polymer segments are associated: association is of intramolecular origin and is due to interaction of long syndiotactic sequences. Prom NMR spectra the motion of associated segments appears as isotropic with and effective correlation frequency 10⁶ – 10⁷ Hz. A globular structure of the associates of s-PMMA is proposed.     

REMOVAL OF CADMIUM BY ANION EXCHANGE IN A WET PHOSPHORIC ACID PROCESS. PART 2: EQUILIBRIA,KINETICS AND REGENERATION

The removal of cadmium by anion exchange from 55 w% H₃PO₄ (black acid from a Nissan H process) at 90^°C in the presence of small amounts of halides (Cl^-, Br^-, I^-) was investigated. Cadmium distribution coefficients, [CD]^resin/[CD]_acid (concentrations in mol/1), larger than 250 were obtained with HBr equilibrium concentrations of more than 0.10 w% in the phosphoric acid solution or with HI concentrations of more than 150 ppm. The regeneration of the Cd loaded resin was performed with a very dilute phosphoric acid solution (< 1 w% H₃PO₄).

The excess of iodide in the phosphoric acid solution could also be- removed by anion exchange. A value of about 90 was obtained for the iodide distribution coefficient of a weakly basic resin. This resin could be regenerated with an 1 M NH₃ solution at 50^°C.

The rate of adsorption and desorption of both cadmium and iodide were mainly determined by the diffusion in the resin|particle. Effective diffusivities of about 3*10^-13 m^Z/s and 1.3*10^-11m^Z/s were obtained for the adsorption of cadmium in the presence of HI and for the adsorption of iodide respectively.     

Shock Tube Study of High-Temperature Reactions of Cyclopentadiene

The thermal decomposition of cyclopentadiene has been studied in the temperature range 1260–1530 K behind reflected shocks. The total pressure ranged from 1.5 to 2.3 bar. Resonance absorption was used to record the temporal concentration profiles of H atoms. This sensitive technique allowed the study of the reaction systems under favorable conditions by applying very low initial concentrations (0.5–8 ppm). For cyclopentadiene decomposition R1, C₅H₆ → C₅H₃-c + H, a rate expression of k₁ = 1.1 × 10¹⁵ exp(–38760/T) s⁻¹ was deduced. In a separate series of experiments the consumption by cyclopentadiene of H atoms, which had been generated by the thermal decay of ethyl iodide, was investigated. A preliminary value of k₂ = 1.4 × 10¹⁴ exp(–2739/T) cm³ mol⁻¹ s⁻¹ was deduced for the total rate of H-atom consumption by cyclopentadiene R2, C₅H₆ + H → products.     

Removal of tin from dilute solutions

The fluidised bed cell of inert glass beads is an electrolytic reactor which is designed to provide higher ion‐transfer conditions during electrolysis, thus enabling metals to be removed efficiently from dilute solutions. The effectiveness of the method as a means of removing metals from effluent to meet discharge consent levels is studied for the in situ removal of tin from dilute solution (concentration range 0.25–1.00 gdm⁻³). The results show that the combination of high mass transport conditions and a moderately high electrode surface area per unit electrode volume provides a system for continuous removal of metal from dilute solutions. The effects of acid concentration, tin concentration, current density, fluidised bed agitation, electrode spacing, type of electrode and lead impurities on the removal of tin are reported and expressed in terms of the percentage removal of tin (α_Sn), the efficiency of tin deposition (ϕ_Sn), and the energy consumption (W_Sn) for 1 kg of tin deposited. The results show that tin can, under optimised conditions, be removed from dilute solutions to a residual concentration of 0.001 gdm⁻³. © 2001 Society of Chemical Industry     

Oxidation of iodide ions by means of cyclic voltammetry

From chronovoltammetric and cyclovoltammetric polarization curves three mechanisms of iodide ions have been established: 3I^? = I^?₃ + 2e,2I^?₃ = 3I₂ + 2e and 2I^? = I₂ + 2e under certain conditions of scan rate, concentration of iodide ions and area of electrode in the aqueous solutions KI (background solution 1 N Na₂SO₄) with half-wave potentials of 0.428, 0.489 and 0.507 V by silver/silver chloride electrode.     

Study of gas–solids flow in a short CFB riser by statistical and chaotic deterministic analysis of optical fibre probe signals

In this work, a short CFB riser with a height of 2.42 m and an ID of 82 mm was operated under different dilute operating conditions to study the fluid dynamics of FCC catalyst particles (d_p = 80 µm, ρ_p = 902 kg/m³) in air. The electrical signals from the optical fibre probe were sampled at a frequency of 1000 Hz for a period of 30 s and were obtained at different positions along the radius and height of the riser. Data were analysed using both statistical methods (time average, standard deviation and frequency distribution) and chaos methods (construction of attractors; correlation dimension, D_ML; and Kolmogorov entropy, K_ML). Some results on solids holdup deduced from the electrical signal are also presented for the developed zone of the riser. It was verified that for very dilute conditions, increasing gas velocity produces more complex and less predictable fluctuations in solids concentration, while increasing solids flux generally reduces complexity and increases predictability. However, results for the most dilute condition used shows that for the radial position where solids holdup is higher (near the wall), the increase in solids concentration does not affect the mean free path of the particles, resulting in higher values of D_ML than in the dilute region (core). © 2012 Canadian Society for Chemical Engineering     

Recovery of platinum group metals from secondary materials. I. Palladium dissolution in iodide solutions

Thermodynamic predictions are reported for platinum and palladium in aqueous ammonia and iodide solutions, to define less aggressive conditions than used hitherto for leaching palladium and platinum from secondary materials. Cyclic voltammetry and amperometry of thin films of palladium, electrodeposited onto rotating vitreous carbon disc electrodes, indicated that partially oxidised adsorbed species passivated dissolution in aqueous ammonium sulfate. By contrast, dissolution rates in aqueous potassium iodide solutions were a significant fraction of that corresponding to the mass transport controlled rate of reduction of tri-iodide, which was demonstrated to be a suitable oxidant for the envisaged metal recovery process. However, iodide concentrations > 1 m were required to achieve adequate solubility of the oxidation products, assumed to be PdI₄²⁻ ions, thereby avoiding inhibition by PdI₂. The reduction of tri-iodide on palladium was very facile, with large exchange current densities and Tafel coefficients; two alternative mechanisms are proposed that fitted experimental results well. In addition, a kinetic model to predict dissolution rates of Pd in tri-iodide solutions gave good agreement with experimental data, provided an equilibrium constant of 10^−4.5 was used for the PdI₂/PdI₄²⁻ reaction, rather than the value of 10^−2.8 derived from thermodynamic data.     

Low‐temperature conversion of spent adsorbent to iodine sodalite by a mechanochemical route

The focus on a ball milling induced conversion as a possible synthesis route of iodine sodalite (Na₈Al₆Si₆O₂₄I₂) from zeolite‐based iodine adsorbents in order to treat a radioactive iodine filter for the off‐gas cleaning during nuclear facilities is presented. A mixture of silver iodide and zeolite 13X as a simulated adsorbent was mechanochemically milled using a laboratory‐scale planetary ball mill. The obtained powders were characterized by X‐ray diffraction to determine the effect of milling time on the conversion of the iodine sodalite. The crystal grain size and the lattice strain of the grounded phases were evaluated. After the ball milling, the milled samples were hydrothermally crystallized to form a sodalite phase with a sodium hydroxide solution for 48 h in an autoclave maintained at 150^°C. The iodine sodalite was successfully obtained after hydrothermal crystallization. A leaching test was carried out for the assessment of the order of iodine leachability and chemical durability under reducing conditions. The leaching amount was found to be low on the orders of 10^?4 ～10^?5 mol dm^?3 in sodium thiosulfate solution. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2441–2447, 2012     

The kinetics of silver iodide film formation on the silver anode

The potentiodynamic formation of AgI films by reaction (1) on an Ag rotating disc electrode was studied and the results were compared to previous work regarding the formation of anodic AgBr and Ag₂S films,

In dilute iodide solutions, a very porous AgI film is formed at a rate controlled by the diffusion of I^? to the electrode surface. At higher iodide concentrations, and particularly in high conductivity supporting electrolytes, a porous AgI film forms at a rate initially limited by ionic migration in solution followed by diffusion of I^? in the pores of the AgI film.In 1 M NaI solutions, when AgI becomes rather soluble, thick granular AgI films form at a rate limited by the solid-state migration of ions in the bulk of the film. On the basis of the low-field model of film growth, the ionic conductivity of these AgI films has been determined to be 8.7 × 10^?5 Scm^?1     

Interaction of lodine with nonionic surfactant and polyethylene glycol in aqueous potassium lodide solution

When a nonionic surfactant, such as hexaoxyethylene glycol dodecyl ethers (6ED) is added to an aqueous iodine solution in the presence of potassium iodide, some spectral changes corresponding to the interaction of iodine-potassium iodide mixture with 6ED are found above the critical micelle concentration (CMC) of 6ED. The absorption maximum bands of complexes formed between 6ED and iodine are significantly different from those formed between 6ED and iodine-potassium iodide mixture in aqueous solution. The complexes of iodic compounds (such as iodine, triiodide ion and polyiodide ion) with 6ED show absorption bands at 390 nm, 370 nm and 385 nm which are assigned to an interaction between iodine-6ED, triiodide ion-6ED and polyiodide ion-6ED, respectively. When the concentration of polyethylene glycol (PEG, MW=200–600) becomes high in aqueous triiodide ion solution, the maximum absorption wavelength of triiodide ion solution also shifts toward 370 nm, similar to that of the triiodide ion-6ED complex. If it is assumed that the absorbance between I₃ ^? and the EO chain in 6ED is the same as that between I₃ ^? and the EO chain of PEG, the concept of effective EO number can be applied to explain the behavior in the absorption spectra among I₃ ^?, 6ED and PEG. Here, the effective EO number is defined as the product of EO chain length and concentration of each 6ED and PEG in the complexes. The effective EO number and concentration of PEG decrease in the triiodide ion-PEG complex as the molecular weight of PEG becomes large. Moreover, the effective EO number and concentration of 6ED are lower than those of PEG at all maximum absorption wavelengths.     

Faradaic rectification studies of two electron charge transfer redox couples at the metal (solid) interface

The Faradaic rectification studies of the two electron charge transfer processes, cationic and anionic redox couples, have been carried out. The mechanism of the iodide—iodine reaction through single charge transfer comprises the following steps, of which reaction (b) is the slowest and controls the rate of overall reactions.

The values of the transfer coefficient and rate constant are obtained for the second step, which is rate determining in both the directions. The values of the parameters obtained when the concentration of the electrochemical species (I₂) is much less in comparison to that of iodide, are α_c = α_a = 0·5 and k^O_a of the order of 5 × 10^?5 cm/s. The parameters for the iodide—iodine reaction, using 1·0 M KNO₃ as supporting electrolyte, are α_c = 0·49, α_a = 0·51 and k^O_a of the order of 5 × 10^?3 cm/s. For the stannous-stannic reaction either of the two steps appears to be rate determining in both directions and the values of the parameters obtained are α_c = 0·48, α_a = 0·52 and k⁰_a = 2·1 × 10^?3 cm/s.     

Reduction of chromate in dilute solution using hydrogen in a GBC-cell

Reduction of metal ions in dilute solutions is of great interest for purification of waste waters and process liquids. Hydrogen gas is a very attractive reductant, since its use gives no additional pollution. In this paper the reduction of chromate in a sulphuric acid medium has been studied. A new electrochemical cell, a GBC-cell, which is a combination of a gas-diffusion electrode in direct contact with a packed bed of carbon particles, is introduced. Hydrogen gas flows along the hydrophobic side of the gas-diffusion electrode and a chromate solution is pumped upwards through the bed. Experiments were carried out with H₂SO₄ solutions initially containing 70 mol m^–3 chromate at various temperatures, solution flow rates, H₂SO₄ concentrations and bed thicknesses. Experimental results for the chromate reduction are described by an empirical relation. It has been found that the reduction of chromate is a first-order reaction in chromate and the apparent rate constant for the chromate reduction increases with decreasing chromate concentration and increasing temperature, H₂SO₄ concentration and bed thicknesses and is practically independent of the flow rate of the solution. It is concluded that the new GBC-cell is very attractive for the reduction of chromate in dilute solutions and for industrial abnlication on a large scale.     

Ion exchange in concentrated media. Correlations for variation of selectivity coefficients with medium

An attempt to relate the different values of the ion-exchange selectivity coefficient in different media is made by considering the two phases as ionic solutions where the activity coefficients of species can be evaluated by means of Mikulin's equation.The selectivity coefficients of the NH₄⁺/H⁺, Na⁺/H⁺, and Li⁺/H⁺ exchanges in a sulfonated cation exchanger and of the NO₃⁻/Cl⁻ exchange in a quaternary ammonium anion exchanger have been measured under different conditions characterized by the degree of crosslinking of the ion exchanger, the water activity of the solution, the concentration ratio of two counterions, and the concentration ratio of a third possible counterion.The water activity of the solution is an essential parameter to be controlled, particularly in dilute or moderately concentrated solutions. A representation of the experimental results on the ion-exchange selectivity coefficient is given in terms of two parameters allowing the selectivity coefficient to be predicted even in very concentrated ionic media.     

Superabsorbent polymeric materials IX: Effect of cationic structure on swelling behavior of crosslinked poly(sodium acrylate‐co‐cationic monomers) in aqueous salt solutions

Two series of xerogels based on sodium acrylate (SA), trimethyl methacrylamidopropyl ammonium iodide (TMMAAI), trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N′‐methylene‐bis‐acrylamide (NMBA) as a crosslinker were prepared by inverse suspension polymerization. The water absorbency and swelling kinetic behavior for these xerogels in water or various saline solutions were investigated. The results showed that the swelling behaviors of these absorbents are related to their chemical structures, their compositions, and the type of external salt solutions. There would be effective improvement in the water absorbency of these two gel series by copolymerizing SA with a small amount of cationic monomer (TMMAAI or TMMAI). The initial absorption rates in deionized water were found to be faster for TM series gels than for TA series gels. The two series of superabsorbents had a tendency to absorb water in dilute nitrate aqueous solutions in the order: Fe³⁺, Ni²⁺, Ca²⁺, Cu²⁺, and Na⁺ for Fe(NO₃)₃, Ni(NO₃)₂, Ca(NO₃)₂, Cu(NO₃)₂, and NaNO₃ aqueous solution, respectively. The absorbency and initial absorption rate for these gels were related to the gel compositions and salt concentrations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1827–1837, 2001     

Study of iodide sorption to the argillite of Tournemire in alkaline media

Argillaceous rocks are considered potential host rocks for radioactive waste repositories. The concrete matrix that could be used as a barrier could react with the groundwater of the geological site, inducing a drastic change in its chemical composition and its pH (10–13). Consequently, the physicochemical properties of the rock in contact with this alkaline solution may be modified and, in turn, may induce modification on the behaviour of radioelements. This study, applied to the argillite of Tournemire, involves characterizing I⁻ sorption to an argillaceous rock in alkaline media in batch experiments under N₂-controlled conditions. I⁻ was added as a ¹²⁵I radiotracer and measured by γ spectrometry.Preliminary experiments were conducted with different solution/solid ratios (v/m=2.5, 5 and 20 ml g⁻¹) and contact times (1–14 days) in order to determine the optimal experimental conditions. The chosen v/m ratio was 5 ml g⁻¹ as the best compromise between a high K_d value and a low error of the measure. The chosen experiment duration was 1 day because I⁻ sorption was highest and to limit the effects of pyrite oxidation. One of the experiments, performed with a radio-sterilized sample to test possible effects from microorganisms, showed that they could enhance iodide retention, particularly during the first 2 contact days.The influence of pH on I⁻ sorption was tested using solutions between values of 8.3 and 12.8. The K_d values were independent of pH and very low (0.3 ml g⁻¹).Finally, the influence of the chemical composition of concrete fluids was also tested. Three solution compositions corresponding to different steps in the evolution of fluids in contact with altering concrete were used: fluid in contact with fresh concrete (pH 13.2), with moderately degraded concrete (pH 12.1) and with strongly degraded concrete (pH 11.5). Each solution contained variable amounts of sodium, potassium, calcium, silica and sulphate. I⁻ sorption was also very low (K_d0.2 ml g⁻¹). Additional experiments were conducted with alkaline solutions containing different amounts of SO₄²⁻ ions (10⁻³–10⁻² M) to test sulphate–iodide sorption competition. I⁻ retention was independent of the sulphate concentration.     

Electrode Kinetics of Solvated Electrons in Liquid Ammonia

Electrode reaction of ammoniated electrons was investigated with voltammetry, potentiometry and chronoamperometry. Experiments were conducted on Pt, Au and W electrodes in 0.5 M LiI, NaI, KI, CsI and KBr solutions of liq. NH₃. The results in dilute solutions (< 10<⁻⁴ M) do not reflect the differences in alkali metal, electrode metal and supporting electrolyte and are explained by a simple one-electron transfer process whose transferring species is a free solvated electron and its ion-pair with a metal cation in a rapid equilibrium. The formal standard potential is −2.155 ± 0.005 V vs. Pb/Pb(NO₃)₂ (0.05 M) at −40°C in liq. NH₃ involving 0.5 M alkali metal iodide. The lower limit of the averaged diffusion coefficient is 0.7 × 10⁻⁴ cm² s⁻¹. At higher metal concentrations (> 10⁻² M), a two-electron transfer process tends to prevail, which is explained by considering the dimer of ion-pairs as the diffusing species.     

Effect of sodium iodide on growth and chemical composition of lucerne and ryegrass

Growth of lucerne was inhibited by sodium iodide even more than that of ryegrass above a concentration equivalent to 1µg cm^–3 of iodine in an applied solution. In sand-culture the extent to which the iodide depressed yield of dry matter depended on the type of nutrient-solution used to stimulate and maintain vigorous growth. In contrast, where the plants were grown in soil the depression was independent of the nutrient-solution used. This difference between solutions is a reflection of the extent to which growing plants can modify pH in the root-zone of a sandy unbuffered substrate and leads to a conclusion that acidity greatly enhances the toxic effect of the iodine. There are reasons for believing that in sunlight iodine may be lost by volatilization even from living plant-tissue. The implication of these findings is discussed in relation to using either iodized fertilizers or iodized salt-blocks in order to maintain iodine in pastoral systems at levels satisfactory for animal-health.     

Corrosion of tin in aqueous solutions of mono-, Di- and trichloroacetic acids

The corrosion behaviour of tin in stagnant mono-, di- and trichloroacetic acids solutions in the pH range 1–6 and at concentrations 4.0 to 5 × 10^?4 M was investigated. The results indicate behaviour that is generally the same but there is some dependence on the acid concentration and the pH value. In 4.0 to 10^?2 M solutions, the corrosion rate (W) increased with increasing acid concentration and decreasing pH value from 1 to 4 as follows: log W=a+b log C, where b=0.70, 0.42 and 0.35 for tri-, di- and mono-chloroacetic acids respectively. At high concentrations 4.0 to 10^?2 M and in the pH range 1–6, the steady state corrosion potential shifted in the negative direction with increase of acid concentration accompanied by an increase in the corrosion rate, indicating that the corrosion process becomes anodically controlled by the complexing of Sn²⁺ ions with organic acid anions and that the order of aggressiveness is mono-<di-<trichloroacetic acids. In dilute solutions (10^?2 to 5.10^?4 M) in the pH range 1–6 the steady state potential shifted in the noble direction with increase of acid concentration (accompanied by a remarkable decrease in the corrosion rate). Corrosion inhibition in dilute solutions was attributed to film formation on the surface of tin which may result from the hydrolysis of tin species.     

Functional polymers and sequential copolymers by phase transfer catalysis

Summary Kinetic analysis of the cationic polymerization of 5-methyl-2-oxazoline (5-MeOZO) was performed with methyl tosylate(MeOTs) and methyl iodide(MeI) initiators by using ¹H NMR spectroscopy. With MeOTs the polymerization of 5-MeOZO proceeded through oxazolinium tosylate species 3 and 4 and the rate constant of propagation (k_p) was determined. With MeI, on the other hand, the propagating ends are present in equilibrium between alkyl iodide (covalent) species 7, 9 and 11 and oxazolinium(ionic) species 6, 8 and 10. Two model reactions enabled to determine the equilibrium constant (K) of 6/7 and to evaluate the reactivity of covalent species 9 (reflected by k_p(c)) and of ionic species 8 (reflected by k_p(i)). Both species 8 and 9 propagate concurrently and contribute to the whole propagation at comparative extents.