Autocatalysis and bistability in the reaction between nitric acid and thiocyanate

The reaction between nitric acid and thiocyanate has been studied both in batch and flow configurations. The batch reaction is autocatalytic with an induction period which is decreased by the addition of HNO₂. At the nitric acid concentrations employed (1–10 M), a red NOSCNH⁺ intermediate is formed. The reaction in a flow reactor exhibits bistability. A model involving competitive reactions of SCN^? and NOSCNH⁺ with NO₂ is suggested, and computer simulations with this model give good agreement with both the batch and flow experiments.     

The reaction of thiocaprylic acid with methyl thiocyanate

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2154–2155, September, 1989.     

Kinetic and product studies on the decomposition of hydroxylamine in nitric acid

The kinetics and stoicheiometry of the decomposition of hydroxylamine in nitric acid have been investigated for the range of conditions where there is a change in function of hydroxylamine from acting as a nitrite scavenger to acting as a generator of nitrous acid. Borderline conditions for this change in function have been identified. Formation of nitrous acid is favoured by increase in [HNO₃], decrease in [NH₃OH⁺] and increase in temperature. Some unusual kinetic phenomena have been observed in the borderline region; the nitrous acid concentration can decrease in the initial stages of reaction, pass through a minimum and then autocatalytically increase to a value greater than the initial value. The results are discussed in terms of the mechanism of reaction.     

Ab initio aqueous thermochemistry: application to the oxidation of hydroxylamine in nitric acid solution

Ab initio molecular orbital calculations were performed and thermochemical parameters estimated for 46 species involved in the oxidation of hydroxylamine in aqueous nitric acid solution. Solution-phase properties were estimated using the several levels of theory in Gaussian03 and using COSMOtherm. The use of computational chemistry calculations for the estimation of physical properties and constants in solution is addressed. The connection between the pseudochemical potential of Ben-Naim and the traditional standard state-based thermochemistry is shown, and the connection of these ideas to computational chemistry results is established. This theoretical framework provides a basis for the practical use of the solution-phase computational chemistry estimates for real systems, without the implicit assumptions that often hide the nuances of solution-phase thermochemistry. The effect of nonidealities and a method to account for them is also discussed. A method is presented for estimating the solvation enthalpy and entropy for dilute aqueous solutions based on the solvation free energy from the ab initio calculations. The accuracy of the estimated thermochemical parameters was determined through comparison with (i) enthalpies of formation in the gas phase and in solution, (ii) Henry's law data for aqueous solutions, and (iii) various reaction equilibria in aqueous solution. Typical mean absolute deviations (MAD) for the solvation free energy in room-temperature water appear to be ~1.5 kcal/mol for most methods investigated. The MAD for computed enthalpies of formation in solution was 1.5-3 kcal/mol, depending on the methodology employed and the type of species (ion, radical, closed-shell) being computed. This work provides a relatively simple and unambiguous approach that can be used to estimate the thermochemical parameters needed to build detailed ab initio kinetic models of systems in aqueous solution. Technical challenges that limit the accuracy of the estimates are highlighted.     

The reaction of atomic oxygen and hydrogen with nitric acid

The reactions have been studied in a discharge-flow system. Kinetic studies were made using resonance fluorescence for the measurement of atom concentrations. Based on the rates of atom loss, the following upper limits were obtained for the rate constants: Observed reaction in the H? HNO₃ system is at least partially due to an autocatalytic chain removal of both reactants. Diagnostic tests have suggested that OH, NO₂, and NO₃ are the chain carriers.     

Indirect determination of ampicillin sodium with sodium nitrate-ammonium thiocyanate-water system by extraction-flotation of cuprous thiocyanate

A novel method for indirect determination of ampicillin sodium by the extraction-flotation is proposed in this paper. It is indicated that the degradation of ampicillin sodium took place in the presence of 0.30 M sodium hydroxide in boiling water for 20 min. At pH 4.0, in the presence of ammonium thiocyanate, the thiol group of the degradation product of ampicillin sodium could reduce copper(II) to copper(I) due to the formation of the emulsion cuprous thiocyanate precipitation. By determining the residual amount of copper(II) in the solution and calculating the flotation yield of cuprous thiocyanate, the indirect determination of ampicillin sodium can be performed. When the concentration of cooper(II) was 5.0 μg/mL, a good linear relationship was obtained between the flotation yield of cuprous thiocyanate and the amount of ampicillin sodium in the range of 0.40～9.6 μg/mL. The linear equation is E = 4.1469 + 3.7949c with the correlation coefficient r = 0.9992, and the detection limit (3σ/K) of 0.37 μg/mL. Each parameter has been optimized and the reaction mechanism has been studied. The method has been successfully applied to the determination of ampicillin sodium in pharmaceutical, human plasma and urine samples. Analytical results obtained are satisfactory.     

Determination of lead by continuous-flow hydride generation and atomic absorption spectrometry: Comparison of malic acid—dichromate,nitric acid—hydrogen peroxide and nitric acid—peroxodisulfate reaction matrices in combination with sodium tetrahydroborate

A continuous-flow hydride generator is combined with a heated quartz tube atomizeratomic absorption spectrometer system for the trace determination of lead. Malic acid K₂Cr₂O₇, HNO₃—H₂O₂ and HNO₃—(NH₄)₂S₂O₃ are all effective for plumbane generation by means of sodium tetrahydroborate. The relative merits of these systems are investigated in terms of sensitivity, efficiency of plumbane generation and interferences. The sensitivities (0.0044 absorbance) obtained under the recommended conditions for the three systems are 3.2, 1.7 and 1.1 ng Pb ml^-1, respectively, whereas plumbane generation efficiencies are 33%, 47% and >80%, respectively, for 1 μg Pb ml^-1. Silver, Au, Cu and Cd interfere seriously in all reaction systems. A dithizone extraction and back-extraction method is utilized to eliminate interfering ions, followed by reduction of the resulting solution in the peroxodisulphate system. The proposed method is applied to water samples and NBS 1566 oyster tissue.     

Study of the interactions of sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate in water+N,N-dimethylformamide mixtures by Raman spectroscopy

Raman spectra of water+N,N-dimethylformamide (DMF) mixtures and their solutions with NaNCS, KNCS and NH(4)NCS were obtained. The bands of nu(CO) stretching, delta(OCN) bending, r(CH(3)) rocking and nu(N-CH)(3)) stretching of the DMF molecule with and without salts were studied. The dependence of the vibration frequencies and Raman intensities of the bands on the composition of the mixed solvent was discussed. The change of the band frequencies as a result of the presence of the salts and the solvation of the cations by the solvent molecules was examined. The stronger cation solvation by the aprotic solvent molecules instead of the water molecules in DMF concentrated solutions was discussed. The nu(CN) and nu(CS) vibrations of the SCN(-) ions were observed as a function of the cation present and the solvent composition. The presence of the SCN(-) ions as "free", contact ion pairs, or solvent separated pairs, was discussed.     

Kinetics and mechanism of the reaction between biacetyl and hydroxylamine in acid solution

The kinetics and mechanism of formation of dimethylglyoxime from biacetyl and hydroxylamine in acid solution have been studied. Unprotonated hydroxylamine was found to react with the hydrogen-bonded carbonyl group to give the conjugate acid of the oxime. Detectable quantities of carbinolamine intermediates were not found in the acid concentration range studied.     

An unusual reaction polymerization in nitric acid medium

We are investigating an unusual reaction that occurs when methyl methacrylate (MMA) is kept in contact with concentrated nitric acid¹ (65% HNO₃, sp. gr. 1.41). Polymer of high molecular weight is formed, showing about one unit of methacrylic acid (MAA) per unit of MMA, when equilibrium is reached. The reaction depends on the temperature, the molar ratio MMA:HNO₃, and the reaction time. Although we also found polymer at temperatures in the range 50–70°C,² in this paper we only report the results when the temperature was kept between 25 and 40°C. Methacrylic acid (MAA) was found to homopolymerize under those mild conditions; its behavior was investigated. Although we also observed that polymer is formed with sulfuric acid (96%) and that acrylic acid polymerizes with both nitric and sulfuric acid at 20–30°C, we are limiting this article to the observed polymerizing action of nitric acid on methyl methacrylate and on methacrylic acid. Work proceeds on this matter in this laboratory.     

Aggregation of sodium dodecylsulfate in aqueous nitric acid medium

Curcumin (Cur) shows low anticancer activity in vivo due to its reduced systemic bioavailability stemmed from its poor aqueous solubility and instability. Suitably functionalized nanocarriers designed to empty the drug specifically at tumor sites can potentially enhance the antitumor activity of Cur. We devised a simple method for the fabrication of water soluble Cur conjugated gold nanoparticles to target various cancer cell lines. Cur was conjugated to hyaluronic acid (HA) to get a water soluble conjugate (HA-Cur). We generated gold nanoparticles (AuNPs) by reducing chloroauric acid using HA-Cur, which played the dual role of a reducing and stabilizing agent and subsequently anchored folate conjugated PEG. These entities were probed using different analytical techniques, assayed the blood compatibility and cytotoxicity. Their interaction with cancer cell lines (HeLa cells, glyoma cells and Caco 2 cells) was followed by flow cytometry and confocal microscopy. Blood-materials interactions studies showed that the nanoparticles are highly hemocompatible. Flow cytometry and confocal microscopy results showed significant cellular uptake and internalization of the particles by cells. HA-Cur@AuNPs exhibited more cytotoxicity comparing to free Cur. The strategy, we adopted here, resulted the formation blood compatible Cur conjugated AuNPs with enhanced targeting and improved efficacy.     

Reducing Pu(IV) to Pu(III) with hydroxylamine in nitric acid solutions

Los Alamos National Laboratory (LANL) has evaluated different techniques to concentrate and remove plutonium from solutions stored at the Rocky Flats Environmental Technology Site (RFETS). Pu(III) oxalate precipitation was chosen to treat nitric acid solutions because it is a simple and efficient technique for removing plutonium. Reducing Pu(IV) to Pu(III) is a key process step which affects the rest of the processing sequence. Because of differences in the literature¹ over the kinetics of the reaction, additional data was obtained and compared with existing data to examine the kinetic relationship, and determine an appropriate relationship for future engineering evaluations. The results and conclusions of this work, along with new experimental data, are presented.     

Nitroxide chemistry XXII. Oxidation of N,N-bis(trifluoromethyl)hydroxylamine

A number of cheap oxidising agents have been found to be effective for the conversion of N,N-bis(trifluoromethyl)hydroxylamine into bis(trifluoromethyl)nitroxide. The best of these are cerium(IV) salts either in the solid state or in aqueous acid solution. Efficient, self-indicating processes have been developed using either catalytic amounts of silver(II) picolinate and aqueous potassium persulphate solutions, or electrochemical oxidation with cerium(III) nitrate and sodium nitrate in dilute nitric acid.     

Predicted reaction rates of H(x)N(y)O(z) intermediates in the oxidation of hydroxylamine by aqueous nitric acid

This work reports computed rate coefficients of 90 reactions important in the autocatalytic oxidation of hydroxylamine in aqueous nitric acid. Rate coefficients were calculated using four approaches: Smoluchowski (Stokes-Einstein) diffusion, a solution-phase incarnation of transition state theory based on quantum chemistry calculations, simple Marcus theory for electron-transfer reactions, and a variational TST approach for dissociative isomerization reactions that occur in the solvent cage. Available experimental data were used to test the accuracy of the computations. There were significant discrepancies between the computed and experimental values for some key parameters, indicating a need for improvements in computational methodology. Nonetheless, the 90-reaction mechanism showed the ability to reproduce many of the trends seen in experimental studies of this very complicated kinetic system. This work highlights reactions that may govern the system evolution and branching behavior critical to the stability of the system. We hope that this analysis will guide experimental investigations to reduce the uncertainties in the critical rate coefficients and thermochemistry, allowing an unambiguous determination of the dominant reaction pathways in the system. Advances in efficient and accurate solvation models that effectively separate entropic and enthalpic contributions will most directly benefit solution-phase modeling efforts. Methods for more accurately estimating activity coefficients, including at infinite dilution in multicomponent mixtures, are needed for modeling high ionic strength aqueous systems. A detailed derivation of the solution-phase equilibrium and transition state theory rate expressions in solution is included in the Supporting Information.     

Radiation-induced decomposition of the tributyl phosphate-nitric acid system: Role of nitric acid

Radiation-induced decomposition of tributyl phosphate-nitric acid as a two-component system has been studied. Degradation products, dibutylphosphoric acid (DBP) and monobutylphosphoric acid (MBP), were determined by separation-extraction method. 0.59, 0.78 and 1.38 are the G (DBP) values and 0.15, 0.17 and 0.13 are the G (MBP) values obtained for pure TBP, TBP-3M HNO₃ extract and TBP-5M HNO₃ extract, respectively. G (–HNO₃) values are 5.19 and 6.15 for 3M HNO₃ and 5M HNO₃ extracts. It is shown that nitric acid plays a significant role in enhancing the decomposition of TBP.     

The reaction of sodium arsenite with sodium chlorite

Existing procedures for the standardisation of sodium chlorite solutions are critically examined and a suitable method detailed. The reaction between sodium chlorite and sodium arsenite solutions is discussed; reaction is quantitative in the presence of sodium bicarbonate and osmic acid as catalyst.     

Newly observed surface-solution oscillating reaction: Mercury-catalyzed dissolution of aluminium in nitric acid

Aluminium metal is dissolved in 3 M HNO₃ with mercury(II) nitrate as a catalyst. Visible oscillations in gas evolution are observed for 2×10^–4 M Hg(NO₃)₂ dissolving solutions. The oscillations are followed quantitatively by monitoring both solution temperature and the intensity of a UV-visible transmittance peak at 369 nm. This peak is attributed to mercury(I) species in solution.