Electrochemical behaviour of phenylethanolamine at gold in aqueous solution

The electrooxidation of phenylethanolamine (2-amino-1-phenylethanol) at a gold electrode in alkaline electrolyte has been studied. Measurement of the differential capacitance of the electric double layer versus the electrode potential has shown that the adsorption of phenylethanolamine at the gold-solution interface plays a significant role in the oxidation mechanism. The effect of amine concentration, electrolyte pH and potential scan rate on the electrooxidation is analysed.     

Light scattering study on the dynamic behaviour of cellulose inclusion complex in LiOH/urea aqueous solution

In our previous study, the rapid dissolution of cellulose in alkali/urea aqueous solution at low temperature induced by a dynamic self-assembly process has been demonstrated [1]. The cellulose solution was meta-stable, and its stability could be influenced by system fluctuations (temperature, concentration or time). In the present work, cellulose dissolved in 4.6wt% LiOH/15.0wt% urea aqueous solution pre-cooled to −12 °C was studied by means of dynamic light scattering (DLS). The results revealed that cellulose existed as single inclusion complexes (ICs) associated with LiOH and urea hydrate which could surround the ICs at their surface. And the ICs were stiff, as revealed by results from transmission electron microscopy (TEM) and light scattering (LS). When there was a system fluctuation, the self-association of cellulose with each other took place, resulted from the destruction of the urea shell, and leading to the aggregation of the ICs. For that reason, the ICs stability could be evaluated by the aggregation behaviour. In our findings, the hydrodynamic radius (R_h,app) for the cellulose dispersion in dilute solution shifted to higher values with an increase of the temperature, the concentration or the storage time, indicating an IC aggregation phenomenon.     

Electrochemical behaviour of copper in aqueous solution containing potassium ethylxanthate

The electrochemical behaviour of copper in aqueous potassium ethylxanthate (KEX) is studied by using potentiodynamic techniques at different sweep rates, complemented with SEM and EDAX. In NaCl solutions a cuprous xanthate film is formed at low potentials, the initial stage of this reaction being the electroadsorption of KEX on copper competing with the adsorption of chloride ions and water. At low surface coverages for electroadsorbed KEX the electrodissolution of copper is partially inhibited as compared to plain NaCl solutions. As the KEX monolayer is completed, a tri-dimensional cuprous xanthate film grows in the electrode surface. On subsequent increase of the applied potential a complex anodic layer is formed leading to copper passivity. Passivity breakdown promoted by either chloride ions or electro-oxidation of the organic film can be observed when the potential exceeds a certain critical value.Facultad de Ciencias Exactas, Universidad Nacional de La Plata.     

Newtonian behaviour of sheared aqueous carboxymethylcellulose solution on aging

The effects of microbiological attack on the rheological properties of sodium carboxymethylcellulose (NaCMC) solutions are described. The effect of aging on the viscosity of aqueous NaCMC solution was studied by means of a Brookfield viscometer. An aqueous NaCMC solution was allowed to age and was subjected to shearing at different time intervals. Dilatant rheological properties were observed in contrast to the usually pseudoplastic behaviour of a normal NaCMC solution. This is attributed to the effect of shear-induced recombination of NaCMC macromolecular crystallites produced as a result of chain scission of NaCMC molecules during aging. The recombination of the crystallites gives higher values of viscosity at higher shear rates. A five months aged sample when subjected to shearing for a period of 20 h exhibits different behaviour. After prolonged post-shearing of this sample, the viscosity measured at shear speeds of 10 rpm and 20 rpm at 72 h and 102h approaches a common value for post-shearing period. The approach to the Newtonian character is attributed to the shear-stress-induced breakdown of the crystalline aggregates. These studies reveal that the aging effects on NaCMC solution have a drastic influence on the rheological properties.     

Synthesis and aqueous solution properties of novel thermosensitive polyacrylamide derivatives

A series of novel thermosensitive polymers were synthesized with acrylamide and thermosensitive macromonomers by radical polymerization in water solution. The structures of the copolymers were characterized by ¹H‐NMR. The effects of the polymer concentration, NaCl concentration, shear rate, and chemical structure on the thermothickening behavior of the polymer solution were investigated by advanced rheometry. The luminous transmittance of the solution with various polymer concentrations was tested by visible spectrometry. The results show that the thermothickening behavior was due to the phase separation of the polymer solution or intramolecular repulsions between the hydrophobic side chains and hydrophilic backbone at high temperatures. Finally, the thermothickening properties of the novel copolymer were studied under conditions simulating an underground oil reservoir. This novel copolymer is expected to be used as an oil‐displacing agent to enhance oil recovery in the future. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 766‐775, 2013     

Studies on viscosity behaviour of concentrated alkali halides in aqueous urea solution

The relative viscosity data of sodium and potassium halides (concentration range 0.125–3 M) in aqueous urea (1.0 M) solution at the temperature 25°, 30°, 35° and 40°C have been determined. The data have been found to satisfy Moulik's equation, for concentrated solution of the alkali halides beyond the Einstein's region. Furthermore the “effective” rigid molar volume V_e and the apparent B coefficient have been computed employing Breslau and Miller treatment from the relative viscosity data. On the basis of apparent B coefficient values obtained for different temperatures, it has been observed that both sodium and potassium halides in aqueous (1.0 M) urea solution show structure breaking trend.     

Electrical conductivity and counterion association of cationic polyacrylamide derivatives in aqueous solution

Equivalent electrical conductivity (Λ) is reported for three series of cationic quaternary ammonium polyacrylamide derivatives with $\hbox{MeSO}_{4}ˆ{‐}$ , Cl⁻, Br⁻ and I⁻ as counterions at 25 °C, the polyion equivalent concentration C ranging from 5.3 × 10⁻⁴ to 6.4 × 10⁻³ N and from 1.0 × 10⁻³ to 1.4 × 10⁻² N. Equivalent electrical conductivity increases with decreasing polyion equivalent concentration, and the sequence of equivalent electrical conductivity Λ of polyelectrolytes for the same series with different counterions in the range of concentration investigated is: $\hbox{MeSO}_{4}ˆ{‐} > \hbox{Cl}ˆ{‐} > \hbox{Br}ˆ{‐} > \hbox{I}ˆ{‐}$ . The plots of the counterion–polyion interaction parameter f and degree of dissociation α of polyelectrolyte versus the polyion equivalent concentration C show that the order of counterion associating or binding to polyions for the same polyelectrolyte series in the range of concentration studied is $\hbox{MeSO}_{4}ˆ{‐} < \hbox{Cl}ˆ{‐} < \hbox{Br}ˆ{‐} < \hbox{I}ˆ{‐}$ . The chemical structures of the polyion have much influence on the Λ, f and α values of the polyelectrolytes. © 1999 Society of Chemical Industry     

Corrosion inhibition of mild steel in neutral aqueous solution by new triazole derivatives

Selected triazole derivatives have been synthesised and evaluated as corrosion inhibitors for mild steel in natural aqueous environment by weight loss, potentiodynamic polarisation and ac impedance methods. All the condensed products showed good inhibition efficiency (IE). The effect of changing functional groups of some triazole derivatives on their inhibition efficiency was also reported using weight loss and potentiodynamic technique. 3-Salicylalidene amino-1,2,4-triazole phosphonate (SATP) was found to be the best corrosion inhibitor compare to the other compounds. Surface analysis was carried out to establish the mechanism of corrosion inhibition of mild steel in neutral aqueous media.     

Electrochemical synthesis and redox behaviour of polypyrrole coatings on copper in salicylate aqueous solution

In this work, polypyrrole (PPy) coatings have been successfully electrodeposited on copper substrates from aqueous salicylate solutions. Homogenous and uniform films can be grown under galvanostatic or potentiostatic control without noticeable substrate dissolution. The redox behaviour obtained for the films is similar to that displayed by PPy grown under the same conditions on noble metals. Strong adherence to copper is observed as far as PPy is in its oxidised state but it is lost when the system is subjected to potentials lower than −0.5 V versus saturated calomel electrode (SCE).     

Thermorheological Simplicity in the Glass Transition

Thermorheological simplicity (TRS) in the glass transition is derived from the principle of temperature (actual and fictive)-time equivalence. Methods of formulating structural relaxation models consistent with TRS are given. Nonlinear dependence of properties on glass structure ( T_f ) and temperature ( T ) is taken into account by modifying the traditional definition of fictive temperature ( T_f ).     

Thermorheological properties of asphalt binders

The rheological properties of different types of asphalt binders were studied and compared considering their constituents and physical characteristics. The saturate, aromatic, resin, and asphaltene (SARA) analysis and differential scanning calorimetry (DSC) have shown their individual constituents and two distinct glass transition temperatures, indicating the phase changes of the two main components of the asphalt binders, namely asphaltenes and maltenes. Rheological characterization was performed over a wide range of temperatures (−10°C-60°C) showing that these materials may exhibit viscoelastic solid to viscous liquid behaviour. Master curves of complex viscosity, storage modulus, and loss modulus were constructed by applying the time-temperature superposition principle, which was found applicable over the temperature range considered. Stress relaxation and steady-shear test were applied to the samples in order to determine their rheological behaviour in the nonlinear viscoelastic regime (viscosity and nonlinear relaxation modulus). The rheological results were modelled and revealed that the Kaye-Bernstein-Kearsley-Zappas (K-BKZ) constitutive equation is suitable in representing the rheological behaviour of asphalts. The SARA analysis and rheological measurements were found to be compatible.     

Rejection of phenolic derivatives in aqueous solution by an interpolymer anionic composite reverse osmosis membrane

Reverse osmosis separation for 23 phenollic derivatives was examined by an anionic charged composite membrane. The solute permeation was carried out in single-solute aqueous solution (200 mg/L) under applied pressure of 3.92–7.85 MPa at 25°C. The correlation between the solute rejection and polar parameters for phenolic derivatives has been investigated. For p-alkylphenols, the solute rejection increased with molecular weight and/or molecular branching. In undissociated state, the rejection of phenolic derivatives was closely related with the Taft's number and the Hammett's number of substituents. Also rejections of phenolic derivatives depended upon the pH value of feed soultion and the polar effect of substituted groups. For example, rejections of aminophenols showed the minimum value at a certain pH value and on either side of the minimum point, the rejection of aminophenol increased. From these facts, the main factors in reverse osmosis serparation by an anionic composite membrane were discussed.     

Electrochemiluminescence of coumarin derivatives induced by injection of hot electrons into aqueous electrolyte solution

Hot electrons can be injected from conductor/insulator/electrolyte (C/I/E) junctions into an aqueous electrolyte solution by cathodic pulse-polarization of the electrode. Injected hot electrons induce electrogenerated chemiluminescence of various luminophores including coumarins in fully aqueous solutions. This is based on the tunnel emission of hot electrons into aqueous electrolyte solution, which can result in the generation of hydrated electrons as reducing mediators. These tunnel-emitted electrons allow also the production of highly oxidizing radicals from added precursors. This work shows that coumarin derivatives are suitable candidates as ECL labels for bioaffinity assays or other analytical applications in which detection is based on the ECL of pulse-polarized C/I/E tunnel-emission electrodes in fully aqueous solutions. The mechanisms of the ECL of coumarins are discussed and the analytical applicability of the ECL of three coumarin derivatives is studied.     

Polymer mixing in aqueous solution

The phase separation behaviour of two polymers (1 and 2) in organic solvents is relatively well understood and is usually due to repulsive interactions between 1 and 2 chain segments. In aqueous solutions, however, where the interaction of the polymer with the solvent is expected to be large, the behaviour is less well understood. In this paper the phase separation of polymers in aqueous solution has been studied and some of the factors which could control the phase separation have been investigated. The volumes of the separated phases were found to be related to the sizes of the polymer/solvent interactions. The polymer with the most positive second virial coefficent was found to occupy the phase with the largest volume. For both miscible and immiscible pairs the mixed second virial coefficients (A₁₂) was assessed from osmotic pressure measurements and was found to be an average of the individual second virial coeffients (A₁₁ and A₂₂). A few polymer pairs were found to mix and this was thought to be caused by hydrogen bonding between 1 and 2 chain segments. Mixtures of rod-like and coiled polymers were expected to phase separate to give a concentrated, ordered phase containing nearly all of the rod-like polymer and a larger phase containing the coiled polymer. However this behaviour was not found when a cellulose derivative (rod-like) was mixed with dextran (flexible).     

Removal of pyridine derivatives from aqueous solution by activated carbons developed from agricultural waste materials

The paper investigates the ability of activated carbons developed from coconut shell to adsorb α-picoline, β-picoline, and γ-picolin from aqueous solution. The developed carbons are designated as SAC (activated carbon derived from coconut shells with out any treatment) and ATSAC (activated carbon derived from acid treated coconut shells). The carbons were, characterized and utilized for the sorption of α-picoline, β-picoline, and γ-picoline at different temperatures, particle size, pH and solid to liquid ratio. All the studies were performed by batch method to determine various equilibrium and kinetic parameters. The Langmuir and Freundlich isotherm models were applied and the Langmuir model was found to best report the equilibrium isotherm data. The adsorption of α-, β-, and γ-picoline followed the pseudo-second order rate kinetics. On the basis of kinetic studies, various rate and thermodynamic parameters such as effective diffusion coefficients, activation energy and activation entropy were evaluated. It was concluded that in majority of cases, the adsorption is controlled by particle diffusion at temperatures 10° and 25 °C while at 40 °C it is controlled by film diffusion mechanism. Similarly at concentrations 25 and 50 mg/l the adsorption was governed by particle diffusion in most of the cases while at >50 mg/l it was film diffusion controlled. The overall capacity of ATSAC was higher than SAC. The sorption capacity of γ-picoline was found more followed by β-picoline and α-picoline.     

Adsorption of some highly toxic dyestuffs from aqueous solution by chitin and its synthesized derivatives

The adsorption of indigo carmine (IC) and trypan blue (TB) by chitin was kinetically investigated as dependent on temperature and pH. Experimental data obtained at different temperatures for the adsorption of each dyestuff were applied to the pseudo first-order, the pseudo second-order and the intraparticle diffusion rate equations, and the pseudo first-order rate constants (k₁), the pseudo second-order rate constants (k₂) and the intraparticle diffusion rate constants (k_p) at these temperatures were calculated, respectively. In addition, adsorption isotherms of each dyestuff by chitin were also determined at different temperatures. It was seen that adsorption isotherms fitted the H type. Chitin was then modified via ring-opening reaction with cyclic acid anhydrides (succinic, maleic and 1,2,4-benzenetricarboxylic) in lithium chloride/N,N-dimethylacetamide. Chitin derivatives obtained were compared according to their capabilities to adsorb IC and TB. It was determined that IC and TB were more adsorbed by chitin modified with 1,2,4-benzenetricarboxylic anhydride (CBA) and chitin modified with maleic anhydride (CMA), respectively. 31.33% of IC (C_o: 300 ppm) by CBA, and 44.29% of TB (C_o: 200 ppm) by CMA were adsorbed. Then, the adsorption of IC by CBA and of TB by CMA was kinetically investigated as dependent on temperature. The constants k₁, k₂ and k_p related to the adsorption of IC by CBA and of TB by CMA were calculated as stated above.     

Polarographic behaviour of dithiodipropionic acid in aqueous—non aqueous solvent mixtures

The polarographic behaviour of dithiodipropionic acid [S₂(CH₂CH₂COOH)₂] (referred to herein as RSSR) has been studied in aqueous and 20% v/v methanol, ethanol, acetonitrile, DMSO and DMF media in the presence of 0.1 MKNO₃ and 0.01% thymol. The effects of changes in pH, concentration of RSSR, mercury pressure and different supporting electrolytes—KNO₃, KCl, NaCl, NaClO₄, (CH₃)₄N.Br and (C₂H₅)₄N.Br—on the wave characteristics have been examined and the mechanism of the electrode reaction has been explained. Reversible and diffusion controlled cathodic waves are obtained both at lower and higher pH values.     

Rheological behaviour of polysaccharide aqueous solutions

Several data relative to the viscosity of water-soluble polysaccharide solutions were collected from the literature and processed by different rheological models. Some relationships between the viscosity of these polymer solutions, their molecular weight and their solution concentrations, were established and their validity checked. Thus, an accurate equation correlating the viscosity and both the shear rate and the solution concentration of different water soluble polysaccharides (xanthan, hyaluronan, carboxymethylcellulose) was deduced on the basis of Cross' model which suggests two domains in which the viscosity is constant, i.e. very low and very high shear rate ranges. Then, an expression relating the zero-shear viscosity (A) and the concentration of their solutions was proposed. Finally, an alternative equation to that of Mark–Houwink correlating the molecular weight and the intrinsic viscosity of the water-soluble polysaccharides studied in this paper was found.     

水溶液中碳酸铈的陈化过程

研究了水溶液中碳酸铈沉淀的陈化过程。以氯化铈、碳酸氢铵为原料制备碳酸铈颗粒，并以扫描电子显微镜观察碳酸铈颗粒的形貌与粒度。实验结果表明：当不经过陈化时，碳酸铈颗粒的粒度约为0、1μm，颗粒基本呈球状，团聚在一起；随着陈化时间的增加，碳酸铈颗粒的粒度逐渐增大；当陈化时间为10h时，碳酸铈颗粒为片状晶体，粒度约为6μm。