Gas diffusion-flow injection determination of total inorganic carbon in water using tungsten oxide electrode

A novel gas diffusion-flow injection method has been developed for the rapid and sensitive determination of total inorganic carbon (TIC) in water. The method is based on the diffusion of CO₂ across gas permeable membrane from a donor stream containing 0.1 M HCl to an acceptor stream of sodium acetate (10⁻⁵ mol l⁻¹ and pH 10). The CO₂ trapped in the acceptor stream passes through an electrochemical flow cell contains a tungsten oxide wire and a silver/silver chloride electrode, where it was sensitively detected. The parameters affecting the sensitivity of the electrode such as buffer concentration, pH, flow rate and injected volume were studied in detail. The electrode response was linear in the concentration range from 5 to 100 μg ml⁻¹ CO₃²⁻ with a correlation coefficient (R²) of 0.998. Precision (R.S.D.) was 1.42% for 20 μg ml⁻¹ standard solution of CO₃²⁻ (n=10). The detection limit was 0.20 μg ml⁻¹ CO₃²⁻. The method was evaluated by the injection of real natural water samples and an average recovery of 100.1% was obtained. The sampling rate was 30 samples h⁻¹. The method is simple, feasible with satisfactory accuracy and precision and thus could be used for monitoring TIC in water.     

Morphogenetic control of calcite crystal growth in sulfonic acid based hydrogels

In this paper the mineralization of CaCO(3) in various hydrogel matrices is presented. Sulfonic acid based hydrogels were prepared by introduction of sulfonate-containing monomers into a polyacrylamide network. The sulfonate content of polyacrylamide-co-vinylsulfonate and polyacrylamide-co-allylsulfonate decreases during elution of the copolymers in demineralized water, indicating insufficient linking of the sulfonate-bearing monomers within the hydrogel. In contrast to this, acrylamidomethylpropanesulfonate (AMPS) effectively copolymerizes with acrylamide (AAm) monomers. To study the influence of spatial arrangement of ionic functional groups within hydrogel networks on the mineralization of CaCO(3), AMPS copolymers with different degrees of AMPS cross-linking were synthesized. For the mineralization experiments the copolymers were placed into a double-diffusion arrangement. Calcite as the thermodynamically stable modification of CaCO(3) was obtained with a particular morphology. The pseudocubic habitus resembles aggregates obtained by mineralization in pure polyacrylamide. However, closer examination of the aggregates by scanning electron microscopy (SEM) shows that the crystal growth in the AMPS copolymers is different from that observed in polyacrylamide. Whereas the morphology of the calcite aggregates could be fine-tuned by using copolymers with different sulfonate content, the spatial distribution of the ionic functional groups alters the course of crystallization. Calcium ions are locally accumulated due to the heterogeneous distribution of functional sulfonate groups within the copolymer network. Thereby the nucleation of calcite is triggered, resulting in enhanced mineralization.     

The Mathematical Theory of Ito Diffusions on Hypersurfaces, with Applications to NMR Relaxation Problems

A mathematical framework for translational Brownian motion on hypersurfaces is presented, using an imbedding of the surface and Ito diffusions in the ambient space. This includes a survey of Ito calculus and differential geometry. Computational methods for time correlation functions relevant to spin relaxation studies on curved interfaces are given, and explicit calculations of time correlation functions and order parameters for a Rippled surface are presented.     

The kinetics of vapor-phase nitration of cellulose 2. Nitration with nitric acid under static conditions

The regularities of vapor-phase nitration of cellulose with HNO₃ under conditions of natural convection and hindered heat removal in the absence of air were studied using the nonisothermal kinetic method. It was established that the nitration rate at the depth of conversion of 0.08 to 0.7 is described by the kinetic law d/dt =k ₁ p/(1+), wherek ₁ = 10^4.49±0.6 exp(–A/RT) s^–1 atm^–1, = 10^{–35.5±15.7}exp(B/RT),A = 36.6±3.8 kl mol^–1, andB = 203±88 kJ mol^–1. The diffusion mechanism of vapor-phase nitration of cellulose, which explains the high value of activation energies, is discussed. The effective diffusion coefficient of HNO₃ in cellulose at 25 °3.7 · 10^–7 cm² s^–1) and the activation energy of diffusion (38.3±4.2 kJ mol^–1) were estimated.For Part 1, see Ref. l.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1981–1985, August, 1996.     

Diffusion of Cesium Ions in Agar Gel Containing Alkali Metal Bromides

The present paper gives an account of different aspects of the tracer diffusion of Cs⁺ ions in alkali metal bromides. We have measured the diffusion coefficients, D, of cesium ions in 1% agar gel medium at 25 ^∘C using a zone-diffusion technique over a concentration range of 5 × 10⁻⁵ to 0.1 mol,dm⁻³. The values of the diffusion coefficients were found to deviate from theory, which are explained on the basis of different types of interactions occurring in the ion-gel-water system. The study is also focused on the effect of alkali metal bromides on the obstruction effect and activation energy for the tracer-diffusion of cesium ions in agar gel medium. It is observed that both parameters, extent of obstruction, ∝, and activation energy, E, decrease with increasing charge density of the cation of the supporting electrolyte. The influence of these trends is explained on the basis of competitive hydration between the ions and agar molecules, and the relative distortion in the water structure that is brought about by these different ions and agar molecules.     

Effect of the Structure of Nonuniform Conducting Polymer Films on Their Electrochemical Impedance Response

Electrochemical impedance spectroscopy is used to characterize thin p-doped polypyrrole (PPy) films in propylene carbonate (PC) solutions and poly(trifluorophenyl)thiophene (PTFPT), in solutions based on sulfolane (SF). It appears that the latter film is much less swelled compared to the former one. One consequence of this difference is that the PTFPT film shows a much higher bulk resistance compared to that for the PPy film. Another important consequence is that the swelling of the PTFPT film is essentially physically non-homogeneous. Two parallel, uncoupled paths, with different chemical diffusion coefficients, model the experimental results adequately. In order to quantify the impedance spectra for both polymer films, we use a model proposed by Rubinstein et al. explaining the difference in the diffusion coefficients of Ru(bpy)^3+/2+ ₃ within a thin Nafion film. The model can also predict the impedance spectra for composite powdery electrodes containing different particle sizes, such as composite cathodes and graphite anodes used in lithium batteries.     

Dynamics of end-grafted polystyrene brushes in theta solvents

The dynamics of the concentration fluctuations in end-grafted polystyrene brushes in a theta solvent (cyclohexane) are probed by evanescent wave dynamic light scattering at different wavevectors q and temperatures. When the solvent quality changes from marginal to poor, the relaxation function C(q, t) exhibits strong effects as compared with the smooth variation of the brush density profile. From a single exponential above 50 °C, C(q, t) becomes a two-step decay function. The fast decay is still assigned to the cooperative diffusion albeit slower than in the good solvent regime whereas the slow nonexponential and nondiffusive process might relate to microsegragated and/or chain dynamics in the present polydisperse brush. The relaxation function of the present three brushes with different grafting density reveals similarities and disparities between wet brushes and semidilute polymer solutions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3590–3597, 2006     

Continuous chemiluminescence determination of formaldehyde in air based on Trautz-Schorigin reaction

A new continuous method for the determination of formaldehyde in air is described. A cylindrical wet effluent diffusion denuder is used for the collection of formaldehyde from air into a thin film of absorption liquid (distilled-deionized water). Formaldehyde in the denuder concentrate is on-line detected employing a chemiluminescence flow method based on a reaction of formaldehyde and gallic acid with hydrogen peroxide in an alkaline solution. The collection efficiency of formaldehyde is quantitative at the air flow rate of 0.5 L min⁻¹ (absorption liquid flow rate of 336 μL min⁻¹). The limit of detection (S/N = 3) is 0.60 μg m⁻³ HCHO (0.49 ppb). The calibration graph is linear up to 300 μg m⁻³ HCHO (244 ppb). The relative standard deviations of chemiluminescence method for 1 × 10⁻⁶ and 5 × 10⁻⁶ M HCHO are 2.87% and 1.49%, respectively. Acetaldehyde interferes negligible, other compounds do not interfere. The method was employed for formaldehyde measurement in ambient air. The comparison measurement illustrates the good agreement of results obtained by proposed method with those obtained by reference fluorimetric method.     

Electrochemical Impedance Analysis of Thermogalvanic Cells

Thermogalvanic cells(also known as thermo-electrochemical cells) that convert waste heat energy to electricity are a new type of energy conversion device. However, the electron transfer kinetics and mass transfer of redox couples have not been thoroughly studied. Here, the ion reaction and charge transport in thermogalvanic cells are investigated by electrochemical impedance analysis. We first propose the detailed impedance model followed experimental verification on three types of electrode materials. Parameters including kinetic rate constants and ion diffusion coefficients for the electrodes are obtained by fitting the impedance data. Our study shows explicitly that impedance analysis can provide useful information on selecting suitable electrode materials for thermogalvanic cells.     

Cathode of a fuel cell with a solid polymer electrolyte: Calculating overall currents in the presence of a gas-diffusion layer

Mathematical apparatus, which makes it possible to perform calculations of the current-voltage characteristics of cathodes of fuel cells with a solid polymer electrolyte in conditions where there are present extraneous diffusion restrictions is proposed. In so doing, the partial pressure of oxygen and the absolute pressure of gas in the gas chamber may assume any values. First of all presented are the results of calculations of the current-voltage characteristics intrinsic to active layers of the air and oxygen cathodes, which are performed under the assumption that the extraneous diffusion restrictions are absent altogether. Thereafter, in the same conditions (at the same parameters that characterize the active layer of a cathode), obtained are results of a calculation of the current-voltage characteristics inherent in the air and oxygen cathodes in the presence of extraneous diffusion restrictions. Afterward there is performed an analysis of the way a gas-diffusion layer restricts the process of generation of current in a cathode and of what measures should be taken in order for the extraneous diffusion restrictions to become less significant.