Cyanogen bromide formation from the reactions of monobromamine and dibromamine with cyanide ion

Cyanide ion (CN-) was found to reactwith monobromamine (NH2Br) and dibromamine (NHBr2) according to the reactions NH2Br + CN- + H20 --> NH3 + BrCN + OH- and NHBr2 + CN- + H20 --> NH2Br + BrCN + OH- with respective reaction rate constants of 2.63 x 10(4) M9-10 s(-1) and 1.31 x 10(8) M(-1) s(-1). These values were found to be 10(5)-10(6) times greater than those for the corresponding reactions between chloramine species and CN-. As a result, bromamines, even if present at relatively low concentrations, would tend to outcompete chloramines in reacting with CN-, and thus, the formation of BrCN would predominate that of ClCN through these reaction mechanisms. The NH2Br reaction was found to be general-acid-catalyzed. The third-order catalysis rate constants for H+, H2PO4-, HPO4(2-), H3BO3, and NH4+ correlated linearly with their corresponding acid dissociation constants, consistent with the Br?nsted-Pedersen relationship. The NHBr2 reaction did not undergo catalysis. A model was developed to predict the concentrations of bromamines over time on the basis ofthe above two reactions with CN- and bromamine formation/decomposition reactions previously reported.     

Kinetics of degradation of sorbic acid in aqueous glycerol solutions

Degradation of sorbic acid in aqueous glycerol solutions at pH 4·0 over the a_w range 0·71–1·00 and the temperature range 40°–60°C was found to follow first-order reaction kinetics and to conform to the Arrhenius equation. Activation energy values obtained were 5·8 kcal mol^?1 and 7·8 kcal mol^?1 for systems at 0·80 a_w with and without added Co⁺⁺, respectively. The rate of sorbic acid degradation was observed to increase with decreasing a_w (i.e. increasing glycerol concentration). The presence of added Co⁺⁺ decreased the rate of sorbic acid breakdown at any particular a_w or temperature. Browning of sorbate solutions during storage was markedly inhibited by Co⁺⁺.     

Kinetics and mechanisms of radiolytic degradation of nitrobenzene in aqueous solutions

Steady-state radiolysis experiments were performed to gain insight into the kinetics and mechanisms of nitrobenzene (NB) degradation in aqueous solutions. The degradation of NB under gamma-ray irradiation followed pseudo-first-order kinetics, and the pseudo first-order rate constant and the initial G value of NB decomposition were functionally related to both the initial NB concentration and the irradiation dose rate. Under oxidative conditions, complete mineralization of NB was achieved, whereas no total organic carbon reduction was observed under reductive conditions. The radiolytic products of NB under various conditions were identified using FTIR and GC-MS analyses. The mechanisms behind the radiolytic degradation of NB under both oxidative and reductive conditions were proposed schematically in light of the degradation products observed. In addition, calculations based on ab initio molecular orbital and density functional theory provided support for the proposed mechanisms and the preferred pathways among all the possible reactions.     

Oligomer formation in evaporating aqueous glyoxal and methyl glyoxal solutions

Glyoxal and methyl glyoxal are common secondary atmospheric pollutants, formed from aromatic and terpene precursors. Both compounds are extremely water-soluble due to dihydrate formation and partition into cloudwater. In this work, FTIR-ATR and mass measurements indicate that both compounds remain primarily in the condensed phase due to oligomer formation when aqueous solution droplets are evaporated, regardless of concentration (> or = 1 mM) or, for glyoxal, droplet evaporation rate. FTIR spectral analyses suggestthat oligomer formation is triggered by conversion from dihydrate to monohydrate forms, which are still nonvolatile but contain reactive carbonyl groups. Methyl glyoxal hemiacetal formation is observed by changes in the C-0/C=0 stretch peak area ratio. The formation of glyoxal oligomers is detected by a dramatic shift of the C-0 stretching peak toward low frequencies. Glyoxal oligomer peaks at 1070 cm(-1), 950 cm(-1), and 980 cm(-1) are assigned to free C-OH stretch, dioxolane-linked C-OC asymmetric stretch, and tentativelyto non-dioxolane-linked C-OC stretches, respectively. Acids have little effect on glyoxal oligomer formation; however, base interrupts oligomer formation by catalyzing glyoxal hydration and disproportionation to glycolic acid. Since glyoxal and methyl glyoxal are commonly found in cloudwater and are expected to remain largely in the aerosol phase when cloud droplets evaporate, this process may be a source of secondary organic aerosol by cloud processing.     

NDMA formation during chlorination and chloramination of aqueous diuron solutions

Formation of the potent carcinogen N-nitrosodimethylamine (NDMA) during chlorine disinfection of water containing secondary amines is now generally acknowledged. The phenylurea herbicide diuron is one of the most widely used herbicides in California, has been frequently detected in California's water sources with a transient nature of appearance, and has a structure that suggests it might be an NDMA precursor. This study sought to quantify the potential for NDMA formation from aqueous diuron solutions under varied chlorine and chloramine conditions. NDMA formation was consistently observed even in the absence of added ammonia, which has usually been the source of the nitroso-nitrogen during chloramination of other precursors. It appears that both nitrogen atoms in NDMA are donated by diuron during chlorination in the absence of added ammonia. For a given chlorine and diuron dose, NDMA formation increased in the order OCl- < NH2Cl < NHCl2, a result consistentwith previous NDMAformation studies. Significant quantities of NDMA (170 ng/L) were produced during dichloramination of diuron using a low dichloramine concentration and a diuron concentration at the upper end of typically detected concentrations in California (20 microg/L), suggesting a need for further investigation to accurately assess the human health risks posed by diuron with respect to NDMA formation potential. A reaction pathway is proposed to provide a possible explanation for NDMA formation from diuron during chlorination or chloramination. The findings in this study identify a specific potential precursor of NDMA formation, one that arises from nonpoint sources. This further highlights the difficulties associated with determining the environmental safety of chemicals and their associated byproducts.     

Kinetics and mechanism of degradation of dichlorvos in aqueous solutions containing reduced sulfur species

Reactions of dichlorvos with five reduced sulfur species (hydrogen sulfide, bisulfide, thiosulfate, thiophenol, and thiophenolate) were examined in well-defined anoxic aqueous solutions to investigate their role in its degradation. Reactions were monitored at varying concentrations of reduced sulfur species over pH range to obtain the second-order reaction rate constants. Experiments at 25 degrees C demonstrated that degradation of dichlorvos promoted by bisufide, thiosulfate, and thiophenolate were of much greater importance than hydrolysis under the experimental conditions in our study. In contrast, hydrogen sulfide and thiophenol were not effective in the degradation of dichlorvos. The activation parameters of the reaction of dichlorvos with bisulfide, thiosulfate, and thiophenolate were also determined from the measured second-order rate constants over a temperature range of 12-50 degrees C. The relative reactivity of the reduced sulfur species decreases in the following order: PhS- > HS- approximately equal to S2O3(2-). When the second-order rate constants at 25 degrees C are multiplied by the environmentally relevant concentration of the reduced sulfur species, predicted half-lives of dichlorvos ranged from hours to days. The results indicated that reduced sulfur species could play a very important role in the chemical fate of dichlorvos in coastal marine environments.     

Bromamine decomposition kinetics in aqueous solutions

The objectives of this study are to investigate the kinetics of bromamine decomposition and to identify the corresponding relevant reactions. Experiments were performed with a stopped-flow spectrophotometer system. Experimental variables investigated included pH (6.5-9.5), bromamines concentration (0.15-0.50 mM), ammonia to bromine ratio (5-100), and phosphate and carbonate buffers concentration (5-40 mM). The experimental results were consistent with a reaction scheme that involved the reversible disproportionation of monobromamine into dibromamine and ammonia (2NH2Br (k1)<=>(k(-1)) NHBr2 + NH3), followed by irreversible decomposition of monobromamine and dibromamine into products (2NHBr2 (k2) --> products and NH2Br + NHBr2 (k3) --> products). The monobromamine disproportionation reaction was found to undergo general acid catalysis, and the two subsequent decomposition reactions were found to experience base catalysis. Experimental results were analyzed for the determination of catalysis terms corresponding to H+, NH4+, H2PO4-, HCO3-, and H2O for rate constants k1 and k(-1); HPO4(2-) and H2O for k2; and OH-, CO3(2-), and H2O for k3. These constants were fitted with the Br?nsted relationship, and the resulting fitting expressions were used to calculate any relevant catalysis rate constants that could not be determined at the range of experimental conditions used.     

水溶液中染料聚醚衍生物的性能

采用表面张力法、荧光光谱法和动态光散射法研究了染料聚醚衍生物在水溶液中的性质,包括表面活性、微极性、临界胶束浓度、单个吸附分子所占面积和胶束动力学直径等,推测了其形成胶束结构形态,并与相应聚醚进行对比.结果表明,染料聚醚衍生物的表面活性比聚醚更高,在质量浓度大于0.5 g/L的水溶液中可形成稳定的动力学直径在50～ 150 nm的胶束,其胶束结构疏松,内部被水分子高度溶胀.     

Photocatalytic oxidation of aqueous ammonia over microwave-induced titanate nanotubes

Characterizations of microwave-induced titanate nanotubes (NaxH(2-x)Ti3O7, TNTs) were conducted by the determinations of specific surface area (S(BET)), X-ray diffraction (XRD), X-ray photoelectron spectroscopic (XPS), ionic coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscopy/ energy dispersive X-ray (SEM/EDX), and high-resolution transmission electron microscopy (HR-TEM). The applied level of microwave irradiation during the fabrication process is responsible for both the intercalation intensity of Na atoms into TNTs and the type of crystallization phase within TNTs, which dominate the efficiency of photocatalytic NH3/NH4+. A pure TNT phase presents no powerful ability toward photocatalytic NH3/ NH4+, while the photocatalytic efficiency can be enhanced with the presence of a rutile phase within TNTs. In addition, the mixture of anatase and rutile phase within P25 TiO2 prefers forming NO3-, whereas TNTs yield higher NO2- amount Regarding the effect of acid-washing treatment on TNTs, the acid-treated TNTs with enhanced ion exchangeability considerably improve the NH3/NH4+ degradation and NO2-/NO3- yields. This result is likely ascribed to the easy intercalation of NH3/ NH4+ into the structure of acid-washing TNTs so that the photocatalytic oxidation of intercalated NH3/NH4+ is not limited to the shielding effect resulting from the overload of TNTs.     

The distribution in the soil of aqueous ammonia injected under grass

In an experiment with grassland, aqueous ammonia containing about 28% N was injected in rows 305 mm apart either in the autumn or in the spring. Two treatments supplied 126 and 502 kg N ha^?1. Soil representing a cross-section of one row was taken 3 days after injecting the ammonia in autumn and 8 or 9 days after injecting in spring. The plots receiving ammonia in the autumn were resampled in spring. The soil was divided into 51 × 51 mm sections and for the samples at the time of injection those sections close to the point of injection were further subdivided. Each section or sub-section was analysed for NH_4?N and NO_3?N. The array of values was used to produce a computer printout from which lines of equal concentration could be drawn by the procedure described in the appendix. With 126 kg N ha^?1 applied, maximum concentrations found were 900–1440 μg N g^?1, and these had decreased to 100 μg g^?1 at 20–30 mm from the area of maximum concentration. Similarly with 502 kg N ha^?1 maximum concentrations were 2360–3340 μg N g^?1 and the concentration had decreased to 100 μg g^?1 at 50 mm from the zone of maximum concentration. Therefore even with the very large application of fertiliser only a small part of the surface rooting zone contained a concentration of ammonia large enough to damage roots or adversely affect root growth. The zone of maximum concentration was always above the point of injection and usually to the side of the centre of the slit indicating that the aqueous ammonia tended to flow up and to one side of the slit, presumably because the soil closed rapidly behind the narrow injection tine. This shows that aqueous ammonia may not necessarily be effectively injected as deeply as the depth of slit might indicate. The soils resampled in the spring showed that much ammonium nitrogen remained, mostly concentrated round the zone of maximum concentration near the point of injection. Some ammonium had nitrified and nitrate was distributed more uniformly than ammonium, some had moved 300 mm deep. Soil containing most ammonia also contained more water than the bulk of soil. This soil was also plastic and structureless and the clay was deflocculated. The extra water may initially have come from the injected aqueous ammonia but was retained because of the changed structure.     

Monoammonium glycyrrhizinate stability in aqueous buffer solutions

The objective of this research is to evaluate the thermal stability of monoammonium glycyrrhizinate. Thermodegradation of solutions of monoammonium glycyrrhizinate at various temperatures (50, 70 and 90°C) was studied. This degradation appeared to follow first-order kinetics independently of temperature and was found to be pH dependent. The experiments revealed an activation energy (E_a) of about 33 kJ mol⁻¹ and a t_90% of about 3 years at 20°C in a pH range from 7 to 9. So it can be concluded that monoammonium glycyrrhizinate is stable in a pH range from 7 to 9. It can be interesting for use in oral care or in food industry. © 1998 SCI.     

Naming and identification of tastes in aqueous solutions

Several taste substances were tested in aqueous solutions; tannic and tartaric acids were found unsuitable as a standard substance for the taste identification. Monosodium glutamate, sodium hydrogen carbonate and potassium chloride were often identified as salty substances even when the subjects were able to distinguish between the tastes. They probably identified the taste as salty owing to the lack of proper terms, and unsufficient experience with tasting monosodium glutamate and sodium hydrogen carbonate as substances possessing defined tastes different from the salty taste.     

Kinetics and modeling of the Fe(III)/H2O2 system in the presence of sulfate in acidic aqueous solutions

This work examined the effect of sulfate ions on the rate of decomposition of H2O2 by Fe(III) in homogeneous aqueous solutions. Experiments were carried out at 25 degrees C, pH < or = 3 and the concentrations of sulfate ranged from 0 to 200 mM ([Fe(III)]0 = 0.2 or 1 mM, [H2O2]0 = 10 or 50 mM). The spectrophometric study shows that addition of sulfate decreased the formation of iron(III)-peroxo complexes and that H2O2 does not form complexes with iron(III)-sulfato complexes. The rates of decomposition of H2O2 markedly decreased in the presence of sulfate. The measured rates were accurately predicted by a kinetic model based on reactions previously validated in NaClO4/HClO4 solutions and on additional reactions involving sulfate ions and sulfate radicals. At a fixed pH, the pseudo-first-order rate constants were found to decrease linearly with the molar fraction of Fe(II) complexed with sulfate. The model was also able to predict the rate of oxidation of a probe compound (atrazine) by Fe(III)/H2O2. Computer simulations indicate that the decrease of the rate of oxidation of organic solutes by Fe(III)/H2O2 can be mainly attributed to the complexation of Fe(III) by sulfate ions, while sulfate radicals play a minor role on the overall reaction rates.     

Viscosity of aqueous solutions of gum ghatti

Gum ghatti contains a soluble gum and an insoluble gel which partially dissolves on boiling. Maceration of the gel in water gives a perfectly stable dispersion which for practical purposes behaves as a solution. The viscosity of the gel dispersion is ca 10–30 times that of the soluble gum. The proportion of gel in four commercial batches of gum ghatti varied from 8 to 23 %. The viscosity of the whole gum dispersion depends largely on the proportion of gel. The viscosity of gum ghatti can be closely controlled by blending to a fixed proportion of gel.     

Interaction of calcium carbonates with lead in aqueous solutions

Pure calcium carbonate (calcite and aragonite) solid materials of different particle size (100-200 microm fragments and millimeter-sized single crystals) were interacted with Pb in aqueous solutions at room temperature under atmospheric PCO2. In the case of the micrometer-sized samples, the macroscopic investigation using a batch-type treatment procedure (solutions between 10 and 1000 mg/L Pb) and ICP-AES, SEM-EDS, and powder-XRD showed that the metal is readily removed from the aqueous media by both materials and indicated the sorption processes (mainly surface precipitation leading to overgrowth of cerussite and hydrocerussite crystals) taking place in parallel with surface dissolution processes. The various processes occurring at the calcium carbonate solid-water interface were clearly distinguished and defined in the case of the millimeter-sized samples interacted with 1000 mg/L Pb using a combination of wet-chemical, in-situ (AFM) and ex-situ (AFM, SEM) microscopic, and surface spectroscopic (XPS, 12C-RBS) techniques. The in-situ AFM data revealed the dissolution processes on the surface of the calcium carbonates and the simultaneous heterogeneous nucleation of lead carbonate phases and confirmed the secondary dissolution of lead carbonate crystals grown epitaxially from the initial nuclei. The XPS spectra confirmed that adsorption of Pb occurs simultaneously to dissolution at short interaction times (less than approximately 10 min, prior to precipitation-nucleation/crystal growth) in the case of both CaCO3 polymorphs and that the calcite surface with adsorbed Pb may have an aragonite-type character. The 12C-RBS spectra indicated that absorption (incorporation of Pb2+ ions) also takes place in parallel at the surface layers of the calcium carbonates, resulting in formation of solid solutions.     

Rheological behaviour of tamarind seed gum in aqueous solutions

Tamarind seed gum as seed polysaccharide from Tamarindus indica L. has been characterized for physicochemical and rheological properties in the present work. The structural analysis determined the presence of glucose:xylose:galactose in a molar ratio of 2.61:1.43:1.The Huggins and Kraemer plots obtained by capillary viscometry gave an intrinsic viscosity of 4.7 dl g⁻¹ and the viscosity average molecular mass was calculated to be 9.18 × 10⁵ g mol⁻¹ using the Mark-Houwink relationship. The steady shear and dynamic viscoelasticity properties of tamarind seed gum in aqueous solutions at different concentrations were investigated at 20 °C using a Haake Rheometer RS75. The tamarind seed gum solutions clearly exhibited shear-thinning flow behaviour at high shear rate and Newtonian region occurred at low shear rate range, however, at higher concentrations, pronounced shear thinning was observed. The value of zero shear viscosity (η₀) was estimated by fitting Cross and Carreau models. The specific viscosity at zero shear rate (η_sp0) was plotted against the coil overlap parameter (C[η]) and the slopes of the lines in the dilute and semi-dilute regions were found to be ∼2.2 and 4.3, respectively. The value of the critical concentration (C^∗) was about 4.23/[η]. While, the mechanical spectra in the linear viscoelastic region of tamarind seed gum solutions showed the typical shape for macromolecular solutions. Plots of η versus γ and η^∗ versus ω were superimposable and hence obey the Cox-Merz rule.     

Factors affecting solubility of calcium lactate in aqueous solutions

Calcium lactate (CaL2) crystal formation on the surface of cheese continues to be a widespread problem for the cheese industry despite decades of research. To prevent those crystals from forming, it is necessary to keep the concentration of CaL2 below saturation level. The limited data available on the solubility of CaL2 at conditions appropriate for the storage of cheese are often conflicting. In this work, the solubility of L(+)-CaL2 in water was evaluated at 4, 10, and 24 degrees C, and the effects of salt and pH at those temperatures were investigated. The effects of additional calcium and lactate ions on solubility also were studied. The results suggested that temperature and the concentration of lactate ions are the main factors influencing the solubility of CaL2, with the other parameters having limited effect.