Controlling the radiation degradation of carboxymethylcellulose solution

In this study, the effects of an irradiation on the viscosity of the carboxymethylcellulose (CMC) solution were investigated, and the methods to control the degradation of the CMC caused by an irradiation were developed. The viscosity of the CMC solution was decreased with an increase in the irradiation dose, but the extent of the degradation by an irradiation was found to decrease with an increase in the CMC concentration in the solution. The dependency of the irradiation sources showed that an electron beam radiation had degraded the CMC less severely than a gamma ray radiation. An addition of vitamin C as a radical scavenger to the solution was shown to be effective in preventing the decrease of the viscosity of the solution. Also, in the case of an irradiation at −70 °C, the decrease of its viscosity was efficiently inhibited. The degradation of CMC in the solution was confirmed by the molecular weight distribution.     

Some investigations for a titrimetric determination of nanomoles of carbon

The ultramicrocoulometric acidimetric titration of carbon dioxide in an aqueous solution was compared with a simple volumetric titration in nonaqueous solution. The lower limit of determination was about 200 and 20 ng carbon, respectively. A determination of organic carbon (as benzoic acid or sucrose) in an aqueous solution takes less than 1 min.     

Viscosity-Temperature Behavior of Hydroxypropyl Cellulose Solution in Presence of an Electrolyte or a Surfactant: A Convenient Method to Determine the Cloud Point of Polymer Solutions

The viscosity of hydroxypropyl cellulose (HPC) solution with or without an additive has been measured continuously as a function of temperature with the help of a vibro-viscometer. The viscosity of the polymer solution showed a gradual decrease initially with increase in temperature until a particular point beyond which there was a sharp decrease in the viscosity, which coincided with the clouding of the solution. The cloud point temperature (CP) of the polymer solution was determined from the first derivative plot of viscosity vs. temperature. Effect of addition of an electrolyte or a surfactant on the CP of HPC solution has also been studied. While a decrease in CP of HPC solution in presence of fluoride, chloride, or bromide ions was observed, presence of iodide or thiocyanide ions led to an increase in the CP. However, presence of an ionic surfactant initially lowered the CP but beyond a particular surfactant concentration a sharp increase in cloud point was observed due to interaction of the surfactant with the polymer. The results suggest that surfactants with longer hydrophobic tail or more hydrophobic groups have more affinity for HPC.     

Thermochemical study of the influence of tetraalkylammonium cation sizes on the interaction of their salts with formamide and carbamide in aqueous solutions

Solutions of tetrahexylammonium salts in mixtures of water with additives of hydrophilic substances formamide and carbamide were studied by the thermochemical method at 298.15 K. The enthalpies of solution of tetrahexylammonium perchlorate were measured by the sedimentation method, and the enthalpies of solution of tetrahexylammonium bromide were calculated. The enthalpic coefficients of pair interaction electrolyte—amide in an aqueous solution were determined. The data obtained were compared with those for te tramethyl- tetraethyl- and tetrabutylammonium salts to study the influence of the tetraalkylammonium cation size on its solvation and interaction with amides in an aqueous solution.     

Theory of nonstationary diffusion growth of gas bubble in the supersaturated solution of gas in liquid

General theory of nonstationary diffusion growth of gas bubble in the supersaturated solution of gas in liquid is constructed using the ideas of similarity and self-similar solutions. The balance between the number of gas molecules in solution and in the bubble that displaces incompressible liquid solvent with an increase in bubble size is taken into account at the material isolation of the solution and the bubble. The dependences of the rate of growth of bubble radius on the solubility of gas and the supersaturation of solution are found. The nonstationary effect of a rapid increase in the rate of bubble growth with an increase in the product of gas solubility and solution supersaturation is elucidated. The upper limit of this product at which bubble growth can be considered as isothermal process is established. The theory is constructed at the arbitrary gas solubility.     

Study of two grafting methods for obtaining a 3-aminopropyltriethoxysilane monolayer on silica surface

In order to establish a 3-aminopropyltriethoxysilane (APTES) grafting procedure with limited number of APTESs noncovalently linked to the silica surface, two different methods of grafting (in acid-aqueous solution and in anhydrous solution) were compared. The grafted surface state was investigated by atomic force microscopy (AFM). The stability of the grafting was checked at different temperatures by AFM. Continuous and plane APTES grafted surfaces were successfully prepared using both grafting preparations. The grafting in an anhydrous solution behaves homogeneously and stably compared to the grafting in an acid-aqueous solution. Moreover, with anhydrous solution, results showed that a unique monolayer of APTES was grafted.     

Effects of nonionic surfactant and associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions

The effect of a low molecular weight nonionic surfactant and an acrylic associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions under steady shear was experimentally investigated. The nonionic surfactant (Tween20), associative thickener (Acrysol TT935) and polyacrylamide (Separan AP30) underwent complex molecular interactions in solution as reflected by rheological measurements. The surfactant also interacted with the glycerol solvent. The addition of surfactant in aqueous glycerol solutions reduced the surface tension, as well as the solution viscosity, at low surfactant concentration. The solution viscosity went through a minimum at certain surfactant concentration, depending on the composition of glycerol/water mixture, before increasing again. Similar behavior was found when the surfactant was added to the polyacrylamide solution, except there was an initial increase in the viscosity before the reduction. The associative thickener, Acrysol TT935 (an anionic acrylic emulsion copolymer) exhibited a strong affinity with polyacrylamide in solution, as indicated by a sharp increase in the solution viscosity. The dilute polyacrylamide solution became highly elastic in the presence of either the nonionic surfactant on the associative thickener. A threestage model was proposed to describe the surfactant/thickener/polymer interactions.     

Synthesis of metallic copper nanoparticles coated with polypyrrole

This paper describes a method for polypyrrole (PPy) coating of metallic Cu nanoparticles in aqueous solution in atmosphere. Colloid solution of Cu nanoparticles was prepared by reducing Cu ions with the use of hydrazine in an aqueous solution dissolving citric acid and cetyltrimethylammonium bromide as stabilizers. The PPy coating was performed by polymerizing pyrrole with the use of hydrogen peroxide as an initiator in an aqueous colloid solution of the Cu nanoparticles. Ultraviolet–visible extinction measurements, transmission electron microscopy observation, and X-ray diffraction measurements revealed that the metallic Cu nanoparticles with a size of 27.6 ± 11.1 nm were coated with PPy. The obtained PPy-coated Cu particles were chemically stable even in atmosphere.     

Determination of sulphide, sulphite and thiosulphate with thallic perchlorate or sulphate

Sulphide, sulphite and thiosulphate can be determined separately or in admixture, with thallic perchlorate or sulphate in acid medium. A sample solution is rendered approximately 0.5 M in acid, 5 ml of 0.05 M KI are added and the solution is titrated to a starch end-point with thallium(III) solution. In another method an acid sample solution is titrated with thallium(III) or iodine solution in the presence of indigo carmine indicator. The end-point is improved in the presence of Co(II).     

Chemical kinetics of reactions in the unfrozen solution of ice

Some reactions are accelerated in ice compared to aqueous solution at higher temperatures. Accelerated reactions in ice take place mainly due to the freeze-concentration effect of solutes in an unfrozen solution at temperatures higher than the eutectic point of the solution. Pincock was the first to report an acceleration model for reactions in ice,1 which successfully simulated experimental results. We propose here a modified version of the model for reactions in ice. The new model includes the total molar change involved in reactions in ice. Furthermore, we explain why many reactions are not accelerated in ice. The acceleration of reactions can be observed in the cases of (i) second- or higher-order reactions, (ii) low concentrations, and (iii) reactions with a small activation energy. Reactions with a buffer solution or additives in order to adjust ion strength, zero- or first-order reactions, or reactions containing high reactant concentrations are not accelerated by freezing. We conclude that the acceleration of reactions in the unfrozen solution of ice is not an abnormal phenomenon.     

Investigation of iodine liberation process in redox titration of potassium iodate with sodium thiosulfate

Potassium iodate is often used as a reference material to standardize a sodium thiosulfate solution which is a familiar titrant for redox titrations. In the standardization, iodine (triiodide) liberated by potassium iodate in an acidic potassium iodide solution is titrated with a sodium thiosulfate solution. The iodine liberation process is significantly affected by the amount of acid, that of potassium iodide added, the waiting time for the liberation, and light; therefore, the process plays a key role for the accuracy of the titration results. Constant-voltage biamperometry with a modified dual platinum-chip electrode was utilized to monitor the amount of liberated iodine under several liberation conditions. Coulometric titration was utilized to determine the concentration of a sodium thiosulfate solution on an absolute basis. Potassium iodate was assayed by gravimetric titration with the sodium thiosulfate solution under several iodine liberation conditions. The liberation process was discussed from the changes in the apparent assay of potassium iodate. The information of the appropriate titration procedure obtained in the present study is useful for any analysts utilizing potassium iodate to standardize a thiosulfate solution.     

Adsorption characteristics of a nanodiamond for oxoacid anions and their application to the selective preconcentration of tungstate in water samples.

A nanodiamond with a mean particle size of 4 nm, which was prepared by the detonation of a nanodiamond, has been characterized and used as a collector for tungstate in water samples. An aqueous solution of nanodiamond was found to be stable over the pH range from 3 to 10. Coagulation of the nanodiamond could be brought about by adding an electrolyte solution. The adsorption characteristics of nanodiamond have been elucidated to be attributable to amino groups on its surface by the elemental-analysis data and the zeta potential measured in weak acid media. The unique adsorption properties of the nanodiamond for oxoacid anions were applied to a selective preconcentration method for tungstate in water samples. An appropriate amount of nanodiamond was added to a sample solution at pH 5 and a calcium chloride solution was added to aggregate nanodiamond. The sample solution was then allowed to stand for 2 h and centrifuged. The nanodiamond was transferred onto a membrane filter, washed with a diluted calcium chloride solution and treated in advance of an ICP-AES measurement by either of the following procedures: (a) redispersion of the nanodiamond into dilute nitric acid with an ultrasonic washer and (b) ashing of the membrane filter and the coagulated nanodiamond at 700 degrees C, followed by a treatment of the ash with hydrochloric and tartaric acids. The average recovery of tungstate from 100-ml artificial river-water was found to be 99% at the 0.25 ppm level with an RSD of 2.2% (n = 3). The concentration factor at present is 10.     

The heat of dissolution of uranyl nitrate in aqueous nitrate solutions

Conclusions A model has been suggested to explain the observed relationship between the measured heats of dissolution of uranyl nitrate in aqueous nitrate solutions and the concentration of the salting-out agent. The model describes the change in the structure of water in the solution with change in its concentration. On the one hand, a destruction of the water structure by ions occurs, which is weakened with increase in the distance from the ion, and leads to such irregularity in the distribution of water molecules in the solution that the mean number of molecules of water in unit volume is increased with increase in the distance from the ions. In experiments on the heat of dissolution this increase leads to increased hydration of the uranyl cation and reduction in the endothermicity of the dissolution with increase in the concentration of the solution. On the other hand, an interaction occurs between the ions of the salting-out agent and the water molecules in the solution, leading to the opposite result: There is an increase in the mean number of water molecules of the solution in unit volume in the direction of these ions. In experiments on the heat of dissolution this is revealed in the dehydration of the uranyl cation, and correspondingly in an increase in the endothermicity of the dissolution with increase in the concentration of the solution. The proposed model is in harmony with data on vapor pressure above the solutions (the relationship between the activity coefficient of the water and the concentration of the solution).Translated from Zhurnal Strukturnoi Khimii. Vol. 3, No. 2, pp. 143–150, March–April. 1962     

Adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution

The adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution were investigated. The adsorbed amounts of lanthanides and the degree of mutual separation of lanthanides increased with an increase in the concentration of lithium chloride in aqueous solution. The group separation of the trivalent actinides and lanthanides was observed. This separation phenomenon is similar in a hydrochloric acid solution. However, the adsorption behavior of lanthanides in lithium chloride is different from their behavior in a hydrochloric acid solution. This fact shows that the adsorption mechanisms of lanthanides in a lithium chloride aqueous solution and in a hydrochloric acid solution are different; the adsorption mechanisms are attributed to the ion exchange in a hydrochloric acid solution, and to the complex formation with pyridine group in a lithium chloride solution.     

Synthesis of some ethyleneimine derivatives of pyrimidine

It has been shown that 2, 6-dichloto-4-methylpyrimidine reacts with ethyleneimine in benzene solution in the presence of triethylamine or in an aqueous alkaline medium with the formation of 6-chloro-2-ethyleneimino-4-methylpyrimidine. The condensation of 2, 6-di-chloro-4-methyl-5-nitropyrimidine with an excess of ethyleneimine and in benzene solution in the presence of triethylamine has given 2, 6-diethyleneimino-4-methyl-5-nitropyrimidine.     

Evaporation dynamics of a binary sessile droplet: Theory and comparison with experimental data on a droplet of a sulfuric-acid solution

Diffusion evaporation of a sessile binary droplet in an atmosphere of a noncondensable carrier gas has been considered. For a droplet consisting of two infinitely miscible liquids, a relation between the current values of solution concentration and volume of the droplet has been derived in an explicit form under the ideal solution approximation. It has been shown that the volume of a sessile binary droplet may, as well as the volume of a free binary droplet, vary nonmonotonically with time. The evaporation of a droplet of an aqueous sulfuric-acid solution has been considered in detail taking into account the nonideality of the solution. Time variations in the volume, base area, and contact angle have been experimentally measured for the sessile droplet of an aqueous sulfuric-acid solution on a hydrophobized substrate. The experimental data obtained at different initial humidities of water-vapor and droplet-solution concentrations have been analyzed within the theory of the stationary isothermal diffusion evaporation of a sessile binary droplet.     

Fluorescent derivatization of nitrite ions with 2,3-diaminonaphthalene utilizing a pH gradient in a Y-shaped microchannel.

The on-chip derivatization of nitrite ions with 2,3-diaminonaphthalene (DAN) utilizing a pH gradient formed in a Y-shaped microchannel was investigated. Nitrite ions react with DAN at low pH, and strongly fluoresced at high pH. Therefore, a reaction at low pH followed by the addition of a strong alkaline solution is the usual procedure in a batch scheme. However, a strong alkaline solution, like an NaOH aqueous solution, erodes the wall of the microchannels in substrates made of glass or polymers, and has not been considered suitable for use in microchannels. We first investigated the derivatization reaction and fluorescent properties of nitrite ions with DAN. We found that the on-chip fluorescent derivatization reaction and detection without the addition of an alkaline solution is possible by controlling the pH values of the nitrite solution and the DAN solution to form a suitable pH gradient by utilizing a buffering effect of triethanolamine solution, which is used as an NO2 gas-absorption medium. These results have suggested the feasibility of novel reaction schemes which can provide the desired products due to a controlled pH gradient in the microchannels, as well as the possibility of an on-site monitoring microchip device for ambient NO2.     

Numerical solution of ordinary differential equations by Fluctuationlessness theorem

This paper presents a numerical method based on Fluctuationlessness Theorem for the solution of Ordinary Differential Equations over appropriately defined Hilbert Spaces. We focus on the linear differential equations in this work. The approximated solution is written in the form of an nth degree polynomial of the independent variable. The unknown coefficients are obtained by setting up a system of linear equations which satisfy the initial or boundary conditions and the differential equation at the grid points, which are constructed as the independent variable’s matrix representation restricted to an n dimensional subspace of the Hilbert Space. An error comparison of the numerical solution and the MacLaurin series with the analytical solution is performed. The results show that the numerical solution obtained here converges to the analytical solution without using too many mesh points.     

Homogeneous precipitation of mullite precursors

The synthesis of mullite powders or gels from an aqueous precursor solution has been studied. The starting solution is made by hydrolyzing TEOS into an aqueous solution of aluminium nitrate. When this solution is sprayed into a solution of ammonia in isopropanol, a nearly monophasic mullite precursor is obtained, whereas if this precipitation is made into an aqueous solution of ammonia, or ammonium carbonate, a diphasic colloidal precipitate is formed. By a slow and homogeneous precipitation in aqueous solution, induced by in-situ generation of ammonia by thermal hydrolysis of urea, a monophasic gel is also obtained. The samples have been studied by DTA, DSC, TGA, XRD and dilatometry.     

Membrane-based solvent extraction for selective removal and recovery of metals

A membrane-based solvent extraction process was developed for selective removal and recovery of metals from aqueous solutions. The process utilizes microporous membranes as an interface between an aqueous solution and organic solvents containing liquid ion exchangers. Metal ions are transported from the aqueous solution to the organic phase at the interface created in the pores of membrane. The organic solvent, which is loaded with metal ions in the extraction module, is regenerated in contact with the stripping solution in the stripping module. One important feature of this process is the stability of the membrane system, which results from using an aqueous—organic separator to remove aqueous solution from the organic circulating line. This process was evaluated for enrichment of copper using solvents containing LIX 64N. The process is applicable to selective recovery of metals from ore leachates or metal-containing wastewater.