Adiabatic compressibility of polyelectrolytes: Effect of solvents on copolymers of vinyl pyrrolidone with acrylic acid and N-dimethylaminoethyl methacrylate

The results of adiabatic compressibility measurements for two copolymers, acrylic acid-vinyl pyrrolidone (AA—VP) and N-dimethylaminoethyl methacrylate-vinyl pyrrolidone (DAM—VP), in three different solvents, namely, water, methanol, and dioxane, have been described. The molecular weight of copolymers was determined by the light scattering method and the IR and NMR spectra of the polymers and copolymers were examined to establish that the alternating acrylic acid–vinyl pyrrolidone and N-dimethylaminoethyl methacrylate–vinyl pyrrolidone structure exists in the copolymers. The AA—VP copolymer behaves as a slightly weaker acid than the homopolymer of acrylic acid, while DAM—VP copolymer is very feebly basic and has the same strength as that of the homopolymer of N-dimethylaminoethyl methacrylate. The reduced viscosity for the two copolymers in aqueous solution is very low (～0.08 dL/g for AA—VP copolymer). In methanol solution AA—VP and DAM—VP copolymers show a decrease of øK^°₂ and øV^°₂ by 61.6 × 10^?4 cc/bar/mol and 8.0 cc/mol, and 191.0 × 10^?4 cc/bar/mol and 20.0 cc/mol, respectively, over that of the values of aqueous solution. The void space around the solute is smaller in methanol than in water, and accordingly this decrease has been attributed to geometric effect. Only one copolymer, DAM—VP is soluble in dioxane, and the values are seen to have increased in this solution by 71.0 × 10^?4 cc/bar/mol and 18.7 cc/mol, respectively, compared to the values obtained from aqueous solution. The experimentally determined øK^°₂ and øV^°₂ for AA—VP and DAM—VP copolymer are 0.6 × 10^?4 cc/bar/mol, and 102.4 cc/mol and ?61.0 × 10^?4 cc/bar/mol, 94.4 cc/mol, respectively, in aqueous solution, and ?12.0 × 10^?4 cc/bar/mol, 211.0 cc/mol and ?203.0 × 10^?4 cc/bar/mol, 191.0 cc/mol, respectively, in methanol solution. In dioxane solution the values for DAM—VP copolymer are 59.0 × 10^?4 cc/bar/mol and 229.7 cc/mol, respectively. These experimentally determined values for AA—VP copolymer show an increase by 0.04 × 10^?4 cc/bar/mol, 4.4 cc/mol and 28.3 × 10^?4 cc/bar/mol, 8.0 cc/mol in aqueous and methanol solution, respectively, compared to calculated values determined on the basis of no interaction between acid and the pyrrolidone group. In contrast, the DAM—VP copolymer shows a decrease of 27.6 × 10^?4 cc/bar/mol and 10.3 cc/mol, 149.3 × 10^?4 cc/bar/mol and 20.2 cc/mol, and 23.0 × 10^?4 cc/bar/mol and 4.1 cc/mol in aqueous, methanol, and dioxane solutions, respectively. In aqueous solution these differences between calculated and observed values have been attributed to a change of water structure around the copolymer chain. A similar effect is responsible for the difference of the values in the methanol solution also. In the dioxane solution the difference is rather small, and the solvent structure has probably not altered much due to the presence of the DAM unit in the chain.     

Eco-friendly tape casting of borosilicate glass/Al2O3 sheets for LTCC applications

This work reports the innovative development of a borosilicate glass/Al₂O₃ tape for LTCC applications using an eco-friendly aqueous tape casting slurry. Polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) were the respective dispersants, while carboxymethyl cellulose (CMC) and styrene acrylic emulsion (SA) were the respective binders. The results showed that PVP was more suitable than PAA as the dispersant for the aqueous casting slurry, and that 1.5 wt% PVP would achieve well dispersion of CABS glass/Al₂O₃ powder in the aqueous slurry. Moreover, a small amount of 2.0 wt% CMC binder could yield smooth CABS glass/Al₂O₃ tapes crack free. A high-quality CABS glass/Al₂O₃ tape with a smooth surface was made from an aqueous slurry containing 1.5 wt% PVP dispersant, 2.0 wt% CMC binder, and 2.0 wt% PEG-400 plasticizer. The density, tensile strength, and surface roughness of the green tape were 2.05 g/cm³, 0.87 MPa, and 148 nm, respectively. The resulting CABS glass/Al₂O₃ composites sintered at 875 °C exhibited a bulk density of 3.14 g/cm³, a dielectric constant of 8.09, a dielectric loss of 1.0 × 10^?3, a flexural strength of 213 MPa, a thermal expansion coefficient of 5.30 ppm/^°C, and a thermal conductivity of 3.2 W m^?1 K^?1, thus demonstrating its broad prospects in LTCC applications.     

Tungsten Trioxide Films with Controlled Morphology and Strong Photocatalytic Activity via a Simple Sol–Gel Route

Novel nanostructured tungsten trioxide (WO₃) films with strong photocatalytic activity, have been prepared by a simple sol–gel route from aqueous peroxopolytungstic acid (PTA) precursor solutions. We demonstrate that films with different morphologies can be synthesized by simply adjusting the pH of this precursor solution using different mineral acids such as HCl and HC1O₄, and that this control of film texture represents a way of optimizing photocurrent yield. The best films produced using these methods generated anodic photocurrents of 3.8 mA/cm² for oxidiation of methanol and 2.2 mA/cm ² for water splitting, under AM1.5 simulated solar illumination.     

Molar volumes of cadmium halides in aqueous dioxane

The apparent molar volume, φ_v, of cadmium chloride, cadmium bromide and cadmium iodide in aqueous dioxane (10%, 20%, 30%) at different temperatures and concentrations are estimated from the densities of the solutions measured by a hydrostatic balance. The φ_v values vary linearly with square root of concentrations. Deviations in the slopes of φ_v versus √C are observed at higher concentrations of the salt and φ_vo, limiting apparent molar volume, have been interpreted in terms of solute-solvent interactions. The φ_vo values varies with temperature and can be represented in the power series of temperature. Structure making/breaking capacity of the electrolyte is inferred from the sign of ?²φ_v/?t² values.     

Poly(lactide‐co‐glycolide) solution behavior in supercritical CO2, CHF3, and CHClF2

Cloud point and solution density data between 20 and 100°C and pressures to 3000 bar are presented for poly(lactide) (PLA) and poly(lactide‐co‐glycolide) (PLGA_x, where the molar concentration of glycolide in the backbone x ranges from 0 to 50 mol %) in supercritical CO₂, CHClF₂, and CHF₃. PLA dissolves in CO₂ at pressures near 1400 bar, in CHF₃ at pressures of 500 to 750 bar, and in CHClF₂ at pressures of 20–100 bar. As glycolide (GA) is added to the backbone of PLGA, the cloud point pressure increases by 50 bar/(mol GA) in CO₂, 25 bar/(mol GA) in CHF₃, and by only 2.5 bar/(mol GA) in CHClF₂. PLGA₅₀ does not dissolve in CO₂ to pressures of 3000 bar whereas it is readily soluble in CHClF₂ at pressures as low as 100 bar at 50°C. In comparison, the increases in cloud point pressure with increasing weight average molecular weight (M_w) are only approximately 2.3 bar/(1000 M_w) for PLGA copolymers in CO₂. The solution densities with all three SCF solvents range from 1.1 to 1.5 g/cm³ and they vary only by a small amount over the 80°C range used to obtain cloud point data. More than likely, the ability of the acidic hydrogen in CHF₃ and CHClF₂ to complex with the ester linkage in PLGA makes these better solvents than CO₂ especially since any change in favorable energetic interactions is magnified due to the liquid‐like densities exhibited by these SCF solvents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1155–1161, 2001     

Residence time distributions and reaction kinetics in a fuel cell anode

A method which treats the fuel cell anode as a chemical reactor is developed to predict fuel cell performance. The method is based on experimentally measured residence time distribution parameters and differential cell kinetic data. The apparatus and experimental technique used to obtain the gas-phase residence time distributions are described. Kinetic data obtained from differential cell tests of the electrodes are used to evaluate an empirical rate expression.Axial dispersion model solutions for flow with volume change are obtained, based on the measured Peclet numbers and empirical rate expressions, and compared with experimental data from operating large high-temperature molten carbonate fuel cells. Agreement between the model and the experimentally determined data is very good, but only for low conversions of the fuel.Notation A cross-sectional area, cm² - C concentration of hydrogen. (g mole/cm³) - c=C/C _o dimensionless concentration of hydrogen - D dispersion coefficient cm²/s - d _e equivalent diameter, cm - F Faraday's constant - I total current, A - J current density, mA/cm² - k reaction rate constant, appropriate units - L length, cm - M number of moles - N =D/UL dispersion number - n order of reaction - n _e number of electrons transferred - –r rate of reaction based on volume of fluid, moles of reactant reacted/ cm³ s - S _e surface of electrode, cm² - T absolute temperature, °K - mean residence time, s - U velocity component in Z direction, cm/s - u = U/U ₀ dimensionless velocity - V _a volume of system, cm³ - V operating voltage, V - v volumetric flow rate, cm²/s - fractional conversion, degree of conversion of hydrogen - y mole fraction of hydrogen - Z space coordinate, cm - z =Z/L fractional length Greek letters coefficient of expansion - _m molar density of fuel, g mole/cm³ - overvoltage, V - dimensional variance, s² - ² dimensionless variance - =V_a/v ₀ space time, s     

Synthesis and characterization of polyacrylic acid/dexy 85 and polyacrylic acid/gum arabic adducts

Polyacrylic acid/gum arabic or polyacrylic acid/dextrin (PAA/GA or PAA/D) adducts were prepared by free radical polymerization of highly concentrated, partially neutralized AA using Na₂S₂O₈/Na₂S₂O₃ redox system in the presence of GA or D. Optimum reaction conditions, viz., AA, 6.76 mol/L; Na₂S₂O₃, 26.87 × 10^?3 mol/L; Na₂S₂O₈, 34.9 × 10^?3 mol/L; degree of neutralization, 20%; temperature, 90°C; and time 30 min, were utilized in preparing two adducts of each substrate (GA or D) at two liquor ratios (LRs; 1.25/1 and 6.3/1 L/K). The four adducts formed, viz., PAA/GA₁, PAA/GA_2, PAA/D₁, and PAA/D₂ (where 1 and 2 refer to the low and high LR, respectively) were found to be water soluble at all proportions. IR spectrum of these adducts confirmed the introduction of the COOH group onto their structures. Rheological properties of 7% aqueous solutions of these adducts, including Na‐alginate (Alg), showed that all are characterized by a non‐Newtonian, shear‐thinning, thixotropic behavior. Within the range of shear rate studied, the apparent viscosities of these solutions followed the descending order: PAA/D₂ > PAA/D₁ > Alg > GA₁ = PAA/GA₂. Completing neutralization (Na form) of adducts to 100% results in a remarkable enhancement of their apparent viscosities, so that they follow the descending order, depending on the shear rate: © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4290–4300, 2006     

Swelling behaviour of poly(α‐hydroxyacrylic acid) gel

Poly(α‐hydroxy acrylic acid) (PHA) and poly(acrylicacid) (PAA) gels were prepared by irradiating the respective 15 wt% aqueous solutions with γ‐rays. Swelling ratios for PHA gel were measured as a function of pH and divalent cation (Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺) concentration C₂ in the external solution to provide a comparison with the results for PAA gels. It was found that the swelling ratio of PHA gel steeply increases between pH 2 and 4, followed by a gradual swelling in the higher pH region. The corresponding steep swelling of PAA gel was observed at pH 3–6. Cation specificity in the equilibrium swelling ratio at a lower C₂ value (1.0 × 10⁻³ M) was approximately consistent with the binding selectivity in the solution system. Typically, the swelling ratio of PHA gel in the presence of Ca²⁺ was significantly lower than in the Mg²⁺ system, while the difference was slight for PAA gel. The response of the swelling ratio to changes in pH and C₂ was analysed as a first order relaxation to estimate the time constants. The (de)swelling kinetics measured by both the pH and C₂ jump were qualitatively interpreted in terms of main‐chain stiffness and intermolecular hydrogen bonding in the respective polymers. © 2000 Society of Chemical Industry     

Preparation of solid polymer electrolyte composites: investigation of the ion-exchange process

The rate of ion-exchange between an aqueous solution of platinum tetramine and a Nafion^® 117 membrane in H⁺ form is studied. Experimental data are collected using extended X-ray absorption fine structure (EXAFS) spectroscopy in dispersive mode. Results are obtained for various platinum tetramine concentrations in the solution and different hydrodynamic regimes at the membrane-solution interface. A shift from a layer diffusion controlled rate (L) to a membrane diffusion controlled rate (M) is observed when the salt concentration and the stirring of the solution are increased. Time dependent fractional concentration in platinum tetramine inside the membrane are computed for the two limiting cases of diffusion (L and M). Good agreement is found between experimental and simulated data. The role of the rate of ion-exchange on the electrochemical performances of electrode-membrane-electrode composites for water electrolysis applications is discussed.List of symbols A surface of the membrane contacting the solution (1.0 cm²) - A _Pt geometrical area of the platinum RDE (cm²) - C _i concentration of species i in the bulk solution (mol cm^–3) - C _i ^/* concentration of species i in the membrane (mol cm^–3) - C ^– sulfonate concentration in the membrane (mol cm^–3) - C ₀ concentration at the membrane-solution interface (mol cm^–3) - D _i diffusion coefficient of species i in the solution (cm² s^–1) - D _i ^/* diffusion coefficient of species i in the membrane (cm² s^–1) - F Faraday (96 500 C mol^–1) - I _L limiting current of diffusion (A) - K equilibrium constant = at equilibrium = 48 (298 K) - l diffusion layer thickness (cm) - L diameter of the cell (1.2cm) - n number of electron exchanged (2) during the electrooxidation of [Pt(NH₃)₄]²⁺ - N _i fractional concentration of species i in the membrane = z _i C _i ^*/C ^– - Re Reynolds number defined as l/ - Sc Schmidt number defined as /D - t _1/2 time at which 50% of the ion-exchange is achieved - velocity of the solution (cm s^–1) - V volume of the membrane (0.01 cm³) - z _i charge beared by species i - kinematic viscosity of the solution (0.0114 cm² s^–1) assumed to be equal to that of pure water at 298 K - membrane thickness (cm) - rotation speed of the RDE (rad s^–1)     

Computer simulation of high-discharge-rate battery systems

Simulations were carried out for a proposed two-dimensional high-discharge-rate cell under load with an interelectrode gap of the order of 100 m. A finite difference program was written to solve the set of coupled, partial differential equations governing the behaviour of this system. Cell dimensions, cell loads, and kinetic parameters were varied to study the effects on voltage, current and specific energy. Trends in cell performance are noted, and suggestions are made for development of cells to meet specific design criteria. Modelling difficulties are discussed and suggestions are made for improvement.Nomenclature A surface area of unit cell (cm²) - A _k conductivity parameter (cm^{2 –1} mol^–1) - b Tafel slope (V) - c concentration (mol cm^–3) - c ₀ concentration of bulk electrolyte (mol cm^–3) - D diffusivity (cm² s^–1) - D _h lumped diffusion parameter (J s cm^–2 mol^–1) - D _s lumped diffusion coefficient (A cm² mol^–1) - E rest potential of electrode (V) - F Faraday constant (96 500 C mol^–1) - i current density (A cm^–2) - I total current for unit cell (A) - i ₀ exchange current density (A cm^–2) - N flux of charged species (mol cm² s^–1) - R gas constant (8.314 J mol^–1 K^–1) - R _ext resistance external to cell () - t time (s) - T temperature (K) - t ₀ transference number - u mobility (cm² mol J^–1 s^–1) - V volume of an element in the cell (cm³) - V _ext voltage external to cell (V) - z charge on an ion - _c concentration overpotential (V) - _s surface overpotential (V) - conductivity (^–1 cm^–1) - stoichiometric coefficient - electric potential in solution (V)     

Characterization of reticulate,three — dimensional electrodes

A study has been made of the mass transfer characteristics of a reticulate, three-dimensional electrode, obtained by metallization of polyurethane foams. The assumed chemical model has been copper deposition from diluted solutions in 1 M H₂SO₄. Preliminary investigations of the performances of this electrode, assembled in a filter-press type cell, have given interesting results: with 0.01 M CuSO₄ solutions the current density is 85 mA cm^–2 when the flow rate is 14 cm s^–1.List of symbols a area for unit volume (cm^–1) - C copper concentration (mM cm^–3) - c _L copper concentration in cathode effluent (mM cm^–3) - c ₀ copper concentration of feed (mM cm^–3) - C ₀ ⁰ initial copper concentration of feed (mM cm^–3) - d pore diameter (cm) - D diffusion coefficient (cm²s^–1) - F Faraday's constant (mcoul me _q ^–1 ) - i electrolytic current density on diaphragm area basis (mA cm^–2) - I overall current (mA) - K _m mass transfer coefficient (cm s^–1) - n number of electrons transferred in electrode reaction (me_q mM^–1) - P ] volumetric flux (cm³s^–1) - Q total volume of solution (cm³) - (Re) Reynold's number - S section of electrode normal to the flux (cm²) - (Sc) Schmidt's number - (Sh) Sherwood's number - t time - T temperature - u linear velocity of solution (cm s^–1) - V volume of electrode (cm³) - divergence operator - void fraction - u/K _m a(cm) - electrical specific conductivity of electrolyte (^–1 cm^–1) - _S potential of the solution (mV) - density of the solution (g cm^–3) - v kinematic viscosity (cm²s^–1)     

Application of FTIR spectroscopy for structural characterization of ternary poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

The FTIR spectroscopic technique was used in the study of ternary polymer–metal complexes containing two polyelectrolytes of opposite charge and metal ions. The structure of the ternary (PAA‐Fe³⁺‐PVP) complexes was examined by following the changes in their infrared spectra. It was found that the shapes of the absorption bands of the resultant compounds are influenced by the presence of Fe³⁺. According to this result it was suggested that two types of structure which differ in the composition are formed, one of which results from the coordination of Fe³⁺ with PAA‐PVP complex and the other is due to the formation of Fe³⁺ polycarboxylate. Comparison between the spectrum of PAA‐PVP complex and those of the compounds resulted from the reaction between the two opposite charged electrolytes, PAA and PVP and each of the divalent metal chlorides NiCl₂, CoCl₂, CuCl₂, and ZnCl₂) led to the conclusion that a reaction took place between the divalent transition metal chlorides and the extent of reaction depends on the nature of metal ions and PAA‐PVP complex. The FTIR spectra of the precipitate resulted from the mixtures of PAA‐PVP and Ni(NO₃)₂ or Sr(NO₃)₂ were investigated. It was noted that the addition of Ni(NO₃)₂ or Sr(NO₃)₂ to the mixture of the electrolytes of PAA and PVP provoked appreciable changes in the characteristic spectral features of the complex resulting from the interaction of the metal ions with the polymer–polymer complex. The FTIR spectra of the precipitate resulted from the reaction between CeCl₃, ErCl₃, and LaCl₃ were also investigated. It was concluded that a reaction took place between the rare earth metals and the PPC. This means that ternary polymer–metal–polymer complexes were formed. The extent of changes in the spectral features differs from metal to metal according to the nature of metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Homogeneous liquid–liquid extraction using perfluorooctanesulfonic acid and calcium and its application to the separation and recovery of vitamin B12

A new phase separation phenomenon was observed in which the perfluorooctanesulfonate ion (PFOS⁻) and calcium ion form an ion‐pair associator and the sedimented liquid phase occurs from the homogeneous aqueous solution. This phenomenon was observed in the neutral pH region at room temperature (25 °C). The optimum concentration conditions for the reagents were [PFOS⁻]_T = 7 × 10⁻³ mol dm^‐3 and [Ca²⁺]_T = 1.1 mol dm^‐3. When these findings were applied to the homogeneous liquid–liquid extraction of vitamin B₁₂, the extraction percentage (E) was 83% and the concentration ratio (ie V_a/V_s, where V_a is the volume of the aqueous phase and V_s is the volume of the sedimented liquid phase) was a maximum of 149. The recovery of vitamin B₁₂ was achieved by adding the propanol–acetone (20 : 80 v/v%) mixed solvent to the sedimented liquid phase; the vitamin B₁₂ precipitated and was filtered. Both the PFOS⁻ and Ca²⁺ were removed by dissolution in the mixed solvent. The recovery percentage of vitamin B₁₂ was 78%. © 1999 Society of Chemical Industry     

A study of blending and complexation of poly(acrylic acid)/poly(vinyl pyrrolidone)

Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T_gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T_g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T_d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T_d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T_1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.     

Adsorption and adhesion of poly(vinyl alcohol) and poly(ammonium acrylate) as organic additives for wet mold processing of Al2O3

Adsorption and adhesion of polyvinyl alcohol (PVA) molecules on Al₂O₃ surfaces in pH 3–10 or 0–0.1 mass% poly(ammonium acrylate) (PAA) aqueous solution was examined using the AFM colloidal probe method. The PVA behavior on the solid surface was estimated using force curve measurements obtained using colloidal probe AFM. Extensions originating from the bridging of PVA between the solid surfaces were observed primarily at less than approximately 200 nm in the pH 3 aqueous solution. The extensions, which were observed at more than approximately 600 nm for pH 6 and 10 aqueous solutions, resulted from different conformations of the PVA molecules. In the PVA–PAA system, the number of extensions decreased by increasing the PAA content. This was not observed in a PAA aqueous solution of greater than 0.1 mass%, which indicates that PAA was adsorbed selectively onto the solid surface. The force curve showed that PAA was more effective than PVA.     

New highly proton-conducting membrane poly(vinylpyrrolidone)(PVP) modified poly(vinyl alcohol)/2-acrylamido-2-methyl-1-propanesulfonic acid (PVA-PAMPS) for low temperature direct methanol fuel cells (DMFCs)

A new type of chemically cross-linked polymer blend membranes consisting of poly(vinyl alcohol) (PVA), 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) and poly(vinylpyrrolidone) (PVP) have been prepared and evaluated as proton conducting polymer electrolytes. The proton conductivity (σ) of the membranes was investigated as a function of cross-linking time, blending composition, water content and ion exchange capacity (IEC). Membranes were also characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), and the differential scanning calorimetry (DSC). Membrane swelling decreased with cross-linking time, accompanied by an improvement in mechanical properties and a small decrease in proton conductivity due to the reduced water absorption. The membranes attained 0.088 S cm⁻¹ of the proton conductivity and 1.63 mequiv g⁻¹ of IEC at 25±2 °C for a polymer composition PVA-PAMPS-PVP being 1:1:0.5 in mass, and a methanol permeability of 6.1×10⁻⁷ cm² s⁻¹, which showed a comparable proton conductivity to Nafion 117, but only one third of Nafion 117 methanol permeability under the same measuring conditions. The membranes displayed a relatively high oxidative durability without weight loss of the membranes (e.g. 100 h in 3% H₂O₂ solution and 20 h in 10% H₂O₂ solution at 60 °C). PVP, as a modifier, was found to play a crucial role in improving the above membrane performances.     

Fourier-transform infrared assay of bile salt-stimulated lipase activity in reversed micelles

A Fourier-transform infrared (FT-IR) spectroscopic method has been developed for assaying the bile salt-stimulated human milk lipase (BSSL, EC3.1) catalyzed hydrolysis of triolein in AOT reversed micelles in iso-octane. At 37°C in 50 mmol dm^?3 AOT the molar absorbtivities for the carbonyl stretching frequencies for triolein (at 1751 cm^?1) and oleic acid (at 1714 cm^?1) were 1646 dm³ mol^?1 cm^?1 and 743 dm^?3 mol^?1 cm^?1, respectively. The rate was linearly dependent upon the concentration of enzyme in the water pool up to 10 mg cm^?3 and maximum activity was observed at a ratio (w₀) of [H₂O]:[AOT] = 16·7. Using these conditions, and in the presence of 10 mmol dm^?3 sodium taurocholate (TC), the derived Michaelis–Menten parameters V_max and K_m were 57·5 μmol min^?1 mg^?1 and 5·53 mmol dm^?3, respectively. These results are compared with those obtained in an oil-in-water microemulsion system and are discussed in terms of the relative partitioning of the enzyme and the substrate in the aqueous and oil phases and the interfacial concentration of the substrate in the two systems.     

Thermal decomposition of potassium persulfate in aqueous solution at 50°C in an inert atmosphere of nitrogen in the presence of acrylonitrile monomer

The rate of thermal decomposition of persulfate in aqueous solution in the presence of acrylonitrile (AN) monomer (M) and of nitrogen, may be written as: in the concentration range of persulfate (1.8 to 18.0) ×10^-3, and of monomer (M), 0.30 to 1.20, mol dm^-3. It was observed that the pH of the solution containing persulfate and monomer did not alter during polymerization if the monomer concentrations were close to its solubility under the experimental conditions. Conductance of the aqueous solutions of persulfate and monomer was found to decrease during the reactions. In an unbuffered aqueous solution containing only persulfate, however, the pH was found to decrease continuously at 50°C with time, while the conductance of the solution was found to increase. The monomer (AN) had no effect on the glass electrodes of the pH meter in aqueous solutions, and also on the electrodes of the conductivity cell. It has been suggested that the secondary or induced decompositions of persulfate were due to the following elementary reactions: where (M_j^· radicals (j = 1 to 10) are water-soluble oligomeric or polymeric free radicals. k_x and k_y at 50°C have been estimated as 1.70 X 10^-5 and 5.08 × 10³ dm³ mol^-1 s^-1, respectively. By measuring pH of freshly prepared persulfate solutions at 25°C, it is suggested that 0.05–0.30% of persulfate reacts molecularly with water (i.e., hydrolysis), as soon as it (10^-3 to 10^-2 mol dm^-3) is added to distilled water (pH 7.0). This hydrolysis was found to be stopped in dilute sulfuric acid solution (pH 3–4).     

Properties of aqueous salt solutions of poly(vinylpyrrolidone). II. Polymer dimensions and thermodynamic quantities

The unperturbed dimensions and thermodynamic parameters of poly(vinylpyrrolidone) (PVP) have been studied in aqueous salt solutions, e.g. phosphates, mono- and dihydrogen phosphates, carbonates, sulphates of sodium and potassium. Values of K₀ ( = [η]_ΘM^-1/2, where [η]_Θ is intrinsic viscosity at the theta temperature and M is molecular weight) with M_w = 78 000 g mol^-1 were found to range from 4·63×10^-4 to 5·56×10^-4 dl g^-1, and root-mean-square end-to-end distances, 〈r²〉₀^1/2, ranging from 1·61×10^-6 to 1·68×10^-6cm were evaluated. Values of the characteristic ratio, C_n, the steric parameter, σ, and the enthalpy and the entropy of dilution parameters, χ_H and χ_S, have also been calculated, and the interaction parameter was found to be χ-0·5<-0·001 for aqueous salt solutions of PVP. ©1997 SCI     

Effect of anodically evolved gas bubbles on the rate of cathodic mass transfer in a vertical cylinder cell

Mass transfer coefficients were measured for the deposition of a copper from acidified copper sulphate solution at a vertical cylinder cathode stirred by oxygen evolved at a coaxial vertical cylinder lead anode placed upstream from the cathode and flush with it. The cathodic mass transfer coefficient was increased by a factor of 2.75–6.7 over the natural convection value depending on the rate of oxygen discharge at the lead anode and height of the cathode. The data were correlated by the equation:J=0.66(F_rR_e)^–0.21 An electrochemical reactor built of a series of vertical coaxial annular cells stirred by the counter electrode gases is proposed as offering an efficient way of stirring with no external stirring power consumption.Nomenclature a, b, c constants - C concentration of copper sulphate, mol cm^–3 - d cylinder diameter, cm - D diffusivity, cm² s^–1 - F Faraday's constant - g acceleration due to gravity, cm² s^–1 - h electrode height, cm - i current density at the oxygen generating anode, A cm^–2 - I _L limiting current density, A cm^–2 - K mass transfer coefficient, cm s^–1 - P gas pressure, atm - R gas constant, atm cm³ mol^–1 K^–1 - T temperature, K - u solution viscosity, poise - V oxygen discharge rate as defined by Equation 9, cm³ cm^–2 s^–1 or cm s^–1 - Z number of electrons involved in the reaction - J mass transferJ factor (S _tS_c ^0.66) - S _t Stanton number (K/V) - S _c Schmidt number (v/D) - S _h Sherwood number (Kh/D) - R _e Reynold's number (/Vh/u) - F _r Froude number (V ² /hg) - G_r Grashof number [gh ³/v² (1–)] - density of the solution, g cm^–3 - kinematic viscosity, cm² s^–1 - void fraction of the gas in the liquid-gas dispersion