An improved procedure for the nitration of benzo‐2,1,3‐selenadiazoles and their reduction to ortho‐phenylenediamines

A method for the nitration of benzo‐2,1,3‐selenadiazoles using nitric acid dissolved in a mixture of methanesulfonic acid and phosphorus pentoxide at room temperature is presented. The S_N2Ar displacement of fluoride that is observed when sulfuric acid is used as solvent is prevented and yields are high. Sodium nitrate could be used in place of nitric acid with no loss in yield. Following nitration, the 2,1,3‐selenadiazole ring is cleaved with hydriodic acid to afford a 3‐nitro‐ortho‐phenylenediamine. The method is applied to the multi‐gram preparation of 4‐fluoro‐3‐nitrobenzene‐1,2‐diamine.     

Adsorption studies of cesium on potassium copper nickel hexacyanoferrate(II) from aqueous solutions

Adsorption of cesium from aqueous solutions on potassium copper nickel hexacyanoferrate(II) (KCNF) has been investigated in batch experiments and optimized as a function of concentration of acids, salts and adsorbate using a radiotracer technique. The results are presented in terms of distribution coefficient, K_d (ml·g^–1). The uptake of cesium obeys a Freundlich adsorption isotherm over the concentration range of 3.7 to 37 mmol·l^–1 with b values of 0.77, 0.68 and 0.56 at temperatures of 293, 313, 333 K, respectively. The Langmuir adsorption isotherm is followed in the concentration range of 15 to 75 mmol·l^–1 in the same temperature range. The values of limiting adsorption concentration (C_m) have been found to be 2.58, 2.44 and 2.32 mmol·g^–1. The heat of adsorption was calculated as 26.43 kJ·mol^–1. The influence of a number of anions and cations on cesium retention has also been studied. Column experiments have been performed and breakthrough have been obtained under different operating conditions. The low cesium capacity of 1.1 mmol·g^–1 has been obtained under dynamic conditions as compared to batch experiments. Desorption of cesium from the column has been achieved (45.4%) by nitric acid solution of 8M concentration at a flow rate of 0.5 ml·min^–1.     

Electronic absorption spectra of V2O5

MO calculations of electronic structure and optical transitions for [VO_n]^{5 ?; 2n} (n = 4, 5, 6) clusters in V₂O₅ monocrystals have been carried out by means of the semiempirical CNDO CI method. Using the calculated results, a complete analysis of V₂O₅ optical data as available in the literature and as obtained in the electroreflectivity experiments presented in this paper is performed. An identification of optical transitions in a wide energy range is presented. The optical properties of vanadium pentoxide are shown to be due to the localized charge transfer electronic transitions in the clusters. The fine structure of optical spectra is connected with the covalent splittings of the vanadium 3d and oxygen 2p atomic levels.     

Extraction of uranium(VI) by bis(hexylsulfinyl)methane

The extraction of uranium(VI) with bis(hexylsulfinyl)methane (BHxSM) from nitric acid aqueous solution has been investigated. It was found that the extraction increased with increasing nitric acid concentration up 8.5 mol/l and then decreased. Extraction distribution ratio also increased with the bis(hexylsulfinyl)methane concentration. The extraction species appear to be UO₂(NO₃)₂ ^.2BHxSM. The influences of temperature, salting-out concentration and oxalate concentration on the extraction equilibrium were also investigated, and the enthalpy of the extraction reaction was obtained. The result shows that the reaction of uranium(VI) extraction with BHxSM is an exothermic one.     

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.     

Liquid-liquid extraction of uranium(VI) with 2-ethylhexyltolylsulfoxide (EHTSO)

The liquid-liquid extraction behavior of 2-ethylhexyltolylsulfoxide (EHTSO) towards uranium(VI) contained in nitric acid aqueous solution has been investigated. It was found that the extraction increases with increasing nitric acid concentration up to 5.0 mol/l and then decreases. Extraction also increases with increasing extractant concentration. The extracted species appears to be UO₂(NO₃)₂ ^.2EHTSO. The influences of temperature, NH₄NO₃ and Na₂C₂O₄ concentrations on the extraction equilibrium were also investigated and the thermodynamic functions of the extraction reaction were obtained.     

Effects of lithium insertion and deinsertion into V2O5 thin films: Optical,structural, and absorption properties

The lithiated/delithiated vanadium pentoxide films deposited by sol‐gel spin coating on indium tin oxide–coated glass substrates were analyzed by sputter‐induced photon spectroscopy, X‐ray diffraction, and optical absorption techniques. First, it is shown that the crystalline structure of V₂O₅ after intercalation remains practically unchanged. Particularly, in the optical spectra during 5 keV Kr⁺ ion bombardment of clean, intercalated, and deintercalated V₂O₅ films, a series of sharp lines and unexpected continuum radiation were observed and well explained. It is also demonstrated that the intercalation and deintercalation of lithium have strong influences on various characteristics of pentoxide vanadium. The interpretations of the obtained results in the 3 experiments—X‐ray diffraction, sputter‐induced photon spectroscopy, and optical absorption techniques—are coherent and complement each other.     

Extraction of Uranium(VI) by N-Octanoylpiperidine in Toluene

The extraction of uranium(VI) from nitric acid by N-octanoylpiperidine (OPPD) in toluene has been investigated at varying concentrations of nitric acid, extractant, salting-out agent LiNO₃ and at different temperatures. The mechanism of extraction is discussed in the light of the results obtained. The extracted species have also been investigated using FT-IR spectrometry. The related thermodynamic functions were calculated.     

Extraction of fission products with 1,2-dichloroethane solutions of hexabromo derivative of cobalt dicarbollide from nitric acid medium

The dependence of the distribution of Cs, Sr, Ba, Eu, Ce between nitric acid solutions and 0.06M hexabromo derivative of cobalt dicarbollide (H⁺BBr ₆ ^– ) in dichloroethane has been investigated upon the concentration of the acid, the extractant and the synergistic additive Slovafol 909. The back-extraction due to the presence of propanol, hydrazine, nitric acid and NH₄NO₃ has been studied. The results were similar to those observed in analogous systems using nitrobenzene as the solvent.     

Batch and dynamic extraction of uranium(VI) from nitric acid medium by commercial phosphinic acid resin,Tulsion CH-96

Batch and dynamic extractions of uranium(VI) in 10⁻³–10⁻²M concentrations in 3–4M nitric acid medium have been investigated using a commercially available phosphinic acid resin (Tulsion CH-96). The extraction of uranium(VI) has been studied as a function of time, batch factor (V/m), concentrations of nitric acid and uranium(VI) ion. Dual extraction mechanism unique to phosphinic acid resin has been established for the extraction of uranium(VI). Distribution coefficient (K _d ) of uranium(VI) initially decreases with increasing concentration of nitric acid, reaches a minimum value at 1.3M, followed by increases in K _d . A maximum K _d value of ∼2000 ml/g was obtained at 5.0M nitric acid. Batch extraction data has been fitted into the linearized Langmuir adsorption isotherm. The performance of the resin under dynamic extraction conditions was assessed by following the breakthrough behavior of the system. Effect of flow rate, concentrations of nitric acid and uranium ion in the feed on the breakthrough behavior of the system was studied and the data was fitted using Thomas model.     

Synergistic extraction of uranium(VI) with tri-n-butyl phosphate and i-butyldodecylsulfoxide

Summary The synergistic extraction of uranium(VI) from aqueous nitric acid solution with a mixture of tri-n-butyl phosphate (TBP) and i-butyldodecylsulfoxide (BDSO) in toluene was investigated. The effects of the concentrations of extractant, nitric acid, sodium nitrate and sodium oxalate on the distribution ratios of uranium(VI) have been studied. The values of enthalpy change for the extraction reactions with BDSO, TBP and a mixture of TBP and BDSO in toluene were -23.2±0.8 kJ/mol, -29.2±1.4 kJ/mol and -30.6±0.6 kJ/mol, respectively. It has been found that the maximum synergistic extraction effect occurs when the molar ratio of TBP to BDSO is close to 1. The composition of the complex of the synergistic extraction is UO₂(NO₃)₂ ^. BDSO ^. TBP.     

Group separation of organic nitrates on a new nitric acid ester NP-LC stationary phase

Summary The synthesis of a nitric acid ester NP-LC stationary phase (organonitrate phase), by nitrating a commercial polyol phase (Serva, Polyol Si 100, 5 μm) with mixed sulfuric-and nitric acid, is reported. The nitric acid ester bond is quite stable towards hydrolysis. To examine its possible use as a stationary phase for the group separation of alkyl nitrates, several bifunctional polar alkyl nitrates (di-nitrates, hydroxy-nitrates, keto-nitrates) have been synthesized. In order to simplify their names a new abbreviating nomenclature for multifunctional organic nitrates is presented. With our new stationary phase it is possible to separate mono-, di-, and hydroxy-nitrates as groups completely, a major advantage in sample preparation in the chemistry of smog formation. However a co-elution of di- and keto-nitrates is observed. A distinction of the latter two organonitrate groups is possible by gas chromatography-mass spectrometric detection (MSD). Apart from the fragment ion NO₂ ⁺ (m/z=46 amu), which is nearly specific for alkyl nitrates, aliphatic di- and keto-nitrates show different characteristic fragment ions.     

N,N,N′,N′-tetrabutylmalonamide as a new extractant for extraction of nitric acid and uranium(VI) in toluene

N,N,N,N-tetrabutylmalonamide (TBMA) was synthesized and used for extraction of uranyl(II) ion from nitric acid media in toluene. The effects of nitric acid concentration, extractant concentration, temperature and salting-out agent (LiNO₃) on distribution coefficients of uranyl(II) ion have been studied. The extraction of nitric acid is also studied. The main adduct of TBMA and HNO₃ is HNO₃. TBMA in 1.0 mol/l nitric acid solution. The 1:2:3 complex of uranyl(II) ion, nitrate ion and TBMA as extracted species is further confirmed by IR spectra of the extraction of uranyl(II) ion with TBMA, and found that the NO ₃ ^– in the extraction species UO₂(NO₃)₂·3TBMA did not participate in coordination of uranyl(II) ion. The values of thermodynamic parameters have also been calculated.     

Extraction of palladium from nitric acid medium by commercial resins with phosphinic acid,methylene thiol and isothiouronium moieties attached to polystyrene-divinylbenzene

Summary Commercially available polystyrene-divinylbenzene (PS-DVB) resins functionalized with isothiouronium (Tulsion CH-95), phosphinic acid (Tulsion CH-96) and methylene thiol (Tulsion CH-97) moieties have been used for separating palladium from nitric acid medium. Extraction of palladium has been studied as a function of time, concentration of nitric acid and palladium. The distribution coefficients (K_d, ml/g) of palladium on sulfur based resins (Tulsion CH-95 and Tulsion CH-97) are higher (5000-10⁴ml/g in 0.1M nitric acid) than on Tulsion CH-96 resin and decrease with increasing concentration of nitric acid. The initial rate of extraction of palladium by Tulsion CH-95 and Tulsion CH-97 resins was very rapid and the time required for the establishment of equilibrium was a function of palladium concentration in the aqueous phase. The rate data could be fitted by a second order rate equation and the magnitude of rate constant for the extraction of palladium by these resins (~10²M^-1. min^-1) decreased in the order of: Tulsion CH-95 > Tulsion CH-97 > Tulsion CH-96. The extraction isotherms of Tulsion CH-95 were fitted by Langmuir adsorption model and the coefficients were obtained by regression. The extraction capacity of palladium on Tulsion CH-95 was found to be ~20 mg/g at 3M nitric acid. Column experiments have been conducted and the data were fitted using Thomas model. A column utilization of 75% was achieved for the extraction of palladium by Tulsion CH-95 resin.     

Extraction chromatographic study on the separation of Am<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> using ethyl-BTP as the extractant

Ethyl-substituted bis-triazinylpyridine (Et-BTP), a nitrogen containing soft-donor extractant, was used in investigations pertaining to the separation of Am³⁺ and Eu³⁺ from dilute nitric acid feed solutions by extraction chromatography using XAD-4 as the inert support, chlorinated dicarbollide as the modifier and 2-nitrophenyloctylether (NPOE) as the diluent. After carrying out a series of experiments, the optimum composition of the extractant mixture for the resin was found out to be 0.1 M Et-BTP and 0.025 M CCD in NPOE. Separation factor values were encouraging to carry out subsequent batch uptake studies at varying nitrate ion concentration which indicated favourable separation behaviour up to NaNO₃ concentration of 2 M. Column studies have been carried out and conditions for elution and separation of Am³⁺ from Eu³⁺ have been found out. Long term stability of the resin was also investigated.     

Kinetics of the oxidation of nitric oxide by chlorine and oxygen in nonaqueous media

The kinetics of the reaction between nitric oxide and chlorine have been investigated in both carbon tetrachloride and glacial acetic acid. The nitric oxide-oxygen reaction has been investigated in carbon tetrachloride. The appearance of product, NOCl or NO₂, was monitored spectrophotometrically at a wavelength of 475 nm for NOCl and 343 nm for NO₂. These measurements were performed using an Amino-Morrow stopped-flow apparatus equipped with a Beckman D U monochromator. The data for both the NO? Cl₂ and NO? O₂ systems could be fitted to the third-order integrated equation and the calculated rate constants were 2.75 × 10³ M^?2 s^?1 and 2.79 × 10⁶ M² s^?1, respectively, at 25.1°C. There was a noted increase in rate constants on changing the solvent from carbon tetrachloride to acetic acid. The likelihood of a termolecular encounter is inherent in the mechanism, however, no real evidence to substantiate either a direct termolecular or a series of two bimolecular steps has been obtained, although a ?7 kcal for ΔH⁰ would support the latter.     

The kinetics of the15N/14N isotopic exchange between nitric oxide and nitric acid

The rate of the¹⁵N/¹⁴N isotopic exchange between NO−HNO₃ at high nitric acid concentration (2–10M) have been measured. The experimental data were obtained by contacting nitric oxide at atmospheric pressure with nitric acid solution labelled with¹⁵N, in a glass contactor.     

Studies on the sorption of Pu(IV) on alumina microspheres from nitric acid-oxalic acid solutions

Sorption of Pu(IV) on alumina microspheres prepared by the sol-gel procedure has been investigated for the recovery of plutonium from nitric acid-oxalic acid solutions. Distribution ratio for Pu(IV) between alumina microspheres and nitric acid-oxalic acid have been determined. The influence of the mode of preparation and heat treatment of these microspheres, on the sorption of Pu(IV) have been investigated. Pu(IV) breakthrough capacities have been determined using a 5 ml bed of alumina with solutions of Pu(IV) in 1M HNO₃+0.05M H₂C₂O₄ and 0.5M HNO₃+0.05M H₂C₂O₄. The elution behavior of Pu(IV) loaded on these microspheres were studied using nitric acid solutions containing different oxidising and reducing agents. Investigations were also carried out to fix the activity in the alumina matrix by heat treatment.     

Dissolution Rates of Barium Nitrate in Water and Weak Nitric Acid Solutions Under Stirred and Stagnant Conditions

Barium nitrate is one of the least soluble metal nitrate phases normally present in the nitric acid based highly active liquor, which will require removal from highly active storage tanks during post-operational clean-out of the Sellafield nuclear site. Laboratory experiments have been carried out to determine the dissolution rate of barium nitrate in water and weak acid solutions. The influence of agitation (solutions being stirred by a paddle at a rate of 0, 40 and 60 revolutions per minute (rpm)), dissolution temperature (20–40 °C), nitric acid concentration (0–1 mol·L^?1) and additional solution nitrate {from Al(NO₃)₃} concentration (0–0.5 mol·L^?1) were investigated. An inscribed central composite experimental design was used for each level of stirred agitation (including unstirred), which allowed non-linear trends and interactions among variables to be statistically determined without carrying out a full factorial experimental array. It was found that the dissolution rate was faster for higher temperature, lower nitric acid concentrations and lower nitrate concentrations. Comparing experiments under like conditions, the barium nitrate dissolution rates at an agitation rate of 40 rpm were on average 56% of those at 60 rpm, while the dissolution rate in the unstirred experiments were on average 0.8% of those at 60 rpm, i.e. two orders of magnitude lower. Hence, the transition from stagnant solution conditions with diffusion controlled transfer of solute from the solid interface to agitated solution conditions was found to be significant. Statistical analysis of the data allowed the derivation of a predictive dissolution rate equation.     

Autocatalytic waves in the nitric acid–formaldehyde system

Propagating reaction fronts generated in the autocatalytic oxidation of formaldehyde by nitric acid have been investigated. The experimental values of the wave velocity ν and those of the maximal reaction rate r_m at a given spatial coordinate have been described by the formulae ν = 2(Dk[CH₂(OH)₂]₀)^1/2 and r_m = 0.247 × k[CH₂(OH)₂]₀², respectively, (D and k constants). Similarities and differences to other nitric acid oxidations have been discussed. © 1995 John Wiley & Sons, Inc.