Granulation of activated sludge in a laboratory upflow sludge blanket reactor

The creation of anoxic granulated biomass has been monitored in a laboratory USB (Upflow Sludge Blanket) reactor with the volume of 3.6 L. The objective of this research was to verify the possibilities of post-denitrification of residual NO₃-N concentrations in treated wastewater (denitrification of 10-20 mg L⁻¹ NO₃-N) and to determine the maximum hydraulic and mass loading of the granulated biomass reactor. G-phase from biodiesel production and methanol were both tested as external organic denitrification substrates. The ratio of the organic substrate COD to NO₃-N was 6. Only methanol was proven as a suitable organic substrate for this kind of reactor. However, the biomass adaptation to the substrate took over a week. The cultivation of anoxic granulated biomass was reached at hydraulic loading of over 0.35 m h⁻¹. The size of granules was smaller when compared with results found and described in literary reports (granules up to 1 mm); however, settling properties were excellent and denitrification was deemed suitable for the USB reactor. Sludge volume indexes of granules ranged from 35-50 mL g⁻¹ and settling rates reached 11 m h⁻¹. Maximum hydraulic and mass loadings in the USB reactor were 0.95 m3 m⁻² h⁻¹ and 6.6 kg m⁻³ d⁻¹. At higher loading levels, a wash-out of the biomass occurred. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

Anoxic granulated biomass and its storage

Laboratory experiments involving shutdown and repeated start-up of a denitrification USB reactor with granulated anoxic biomass were conducted in order to find suitable conditions for a safe storage period of the biomass. Anoxic granulated biomass stored under anaerobic conditions for a half year period at 6°C and for a half month period at 18–20°C retained its activity and granular morphology. Storage of anoxic granules under anaerobic conditions for a half year period at 18–20°C led to the loss of the biomass original activity and a significant portion of the granules disintegrated. Anoxic granulated biomass stored for a one and a half month period under endogenous anoxic conditions at 18–20°C retained its activity and granular morphology. A two month storage under endogenous anoxic conditions at 18–20°C was too long and the shutdown of the reactor had to be followed by repeated anoxic granulation. Minimum loading of the USB reactor with N-NO₃ to maintain endogenous anoxic conditions in the sludge bed was in the range of 0.06–0.1 kg of N-NO₃ per m³ per day. Restart of the USB reactor can be accelerated by an addition of anaerobic granulated biomass.     

Anaerobic baffled reactor treatment of biodiesel-processing wastewater with high strength of methanol and glycerol: reactor performance and biogas production

Biodiesel-processing factories employing the alkali-catalyzed transesterification process generate a large amount of wastewater containing high amount of methanol, glycerol, and oil. As such, wastewater has high potential to produce biogas using anaerobic treatment. The aim of this research was to investigate the performance of an anaerobic baffled reactor for organic removal and biogas production from biodiesel wastewater. The effect of different organic loading rates, varying from 0.5 kg m⁻³ d⁻¹ to 3.0 kg m⁻³ d⁻¹ of chemical oxygen demand, was determined using three 22 L reactors, each comprising five separate compartments. Wastewater was pretreated with chemical coagulants to partially remove oil prior to experimentation. Results show that the anaerobic baffled reactor operated at 1.5 kg m⁻³ d⁻¹ of chemical oxygen demand and ten days of hydraulic retention time provided the best removal efficiencies of 99 % of chemical oxygen demand, 100 % of methanol, and 100 % of glycerol. Increasing the organic loading rate over 1.5 kg m⁻³ d⁻¹ of chemical oxygen demand led to excessive accumulation of volatile fatty acids thereby making the pH drop to a value unfavorable for methanogenesis. The biogas production rate was 12 L d⁻¹ and the methane composition accounted for 64–74 %. Phase-separated characteristics revealed that the highest chemical oxygen demand removal percentage was achieved in the first compartment and the removal efficiency gradually decreased longitudinally. A scanning electron microscopic study indicated that the most predominant group of microorganisms residing on the external surface of the granular sludge was Methanosarcina.     

Pilot-Scale Experiment for Simultaneous Dioxin and NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Removal from Garbage Incinerator Emissions Using the Pulse Corona Induced Plasma Chemical Process

A pilot-scale pulse corona induced plasma chemical process (PPCP) reactor for controlling gas-phase dioxins and NO _x simultaneously is installed in a garbage incineration plant. The flow rate of the sampled flue gas is 5,000 Nm³/h (N: standard state) in maximum at the PPCP reactor, which consists of 22 wire-cylinder electrodes and is energized by a 50 kW nanosecond pulse high voltage generator. With an applied plasma energy density of 2.9–6.1 Wh/Nm³, the decomposition efficiency for dioxins is 75–84% based on TEQ (toxic equivalents); the conversion efficiency of NO to NO₂ is ~93% at maximum. The flue gas treated by the PPCP reactor is introduced at a rate of 50 Nm³/h to a wet-type chemical reactor, which uses an aqueous solution of sodium sulfite (Na₂SO₃). More than 90% of NO _x is reduced to nitrogen, with negligible byproducts such as NO₂ ⁻ or NO₃ ⁻ ions left in the solution.     

Anaerobic-anoxic-aerobic sequential degradation of synthetic wastewaters

This study was conducted in a continuous three-stage system of anaerobic (R1)-anoxic(R2)-aerobic (R3) reactors with synthetic wastewater containing phenol (1000 mg/L), chemical oxygen demand (COD) (3000 mg/L), CN⁻ (30 mg/L), SCN⁻(400 mg/L), and NH ₄ ⁺ -N (600 mg/L) as principal pollutants and well-acclimated heterogeneous microbial cultures. The final effluent was partially returned to R2 with a recycle ratio of 1. Anaerobic stage served to detoxify the feed by removing up to 80% of cyanide. Complete SCN⁻ removal and denitrification could be achieved in the anoxic stage by utilizing phenol as an internal source of carbon. Nitrification efficiency of 93% was obtained in the aerobic reactor. The results demonstrated that the three-stage system can give the desired final treated effluent quality (0 mg/L of phenol, 0.2 mg/L of CN⁻, 210 mg/L of COD, and 20 mg/L of NH ₄ ⁺ -N) and that the NO ₃ ⁻ -N concentration can be lowered by a higher recycle ratio.     

Compactin Production Studies Using <Emphasis Type="Italic">Penicillium brevicompactum</Emphasis> Under Solid-State Fermentation Conditions

In the present study, compactin production by Penicillium brevicompactum WA 2315 was optimized using solid-state fermentation. The initial one factor at a time approach resulted in improved compactin production of 905 μg gds⁻¹ compared to initial 450 μg gds⁻¹. Subsequently, nutritional, physiological, and biological parameters were screened using fractional factorial and Box–Behnken design. The fractional factorial design studied inoculum age, inoculum volume, pH, NaCl, NH₄NO₃, MgSO₄, and KH₂PO₄. All parameters were found to be significant except pH and KH₂PO₄. The Box–Behnken design studied inoculum volume, inoculum age, glycerol, and NH₄NO₃ at three different levels. Inoculum volume (p = 0.0013) and glycerol (p = 0.0001) were significant factors with greater effect on response. The interaction effects were not significant. The validation study using model-defined conditions resulted in an improved yield of 1,250 μg gds⁻¹ compactin. Further improvement in yield was obtained using fed batch mode of carbon supplementation. The feeding of glycerol (20% v/v) on day 3 resulted in further improved compactin yield of 1,406 μg gds⁻¹. The present study demonstrates that agro-industrial residues can be successfully used for compactin production, and statistical experiment designs provide an easy tool to improve the process conditions for secondary metabolite production.     

Optimization of culture parameters for production of podophyllotoxin in suspension culture of Podophyllum hexandrum

The root explants of the germinated seedlings of Podophyllum hexandrum were grown in MS medium supplemented with indole acetic acid (IAA) (2 mg/L) and activated charcoal (0.5%), and healthy callus culture was obtained after incubation for 3 wk at 20°C. The cultivation of plant cells in shake flask was associated with problems such as clumping of cells and browning of media, which were solved by the addition of pectinase and polyvinylpyrrolidone. The effect of major media components and carbon source was studied on the growth and podophyllotoxin production in suspension culture. It was found that glucose was a better carbon source than sucrose and that NH₄ ⁺:NO₃ ⁻ ratio (total nitrogen concentration of 60 mM) and PO₄ ³⁻ did not have much effect on the growth and product formation. The relative effect of culture parameters (inoculum level, pH, IAA, glucose, NH₄ ⁺:NO₃ ⁻ ratio, and PO₄ ³⁻) on the overall growth and product response of the plant cell suspension culture was further investigated by Plackett-Burman design. This indicated that inoculum level, glucose, IAA, and pH had significant effects on growth and production of podophyllotoxin. To identify the exact optimum concentrations of these parameters on culture growth and podophyllotoxin production, central composite design experiments were formulated. The overall response equations with respect to growth and podophyllotoxin production as a function of these culture parameters were developed and used to determine the optimum concentrations of these parameters, which were pH 6.0, 1.25 mg/L of IAA, 72 g/L of glucose, and inoculum level of 8 g/L.     

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X??=?NO3?, CF3SO3?, ClO4?, BF4?, and PF6?)

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag₂(X) _m (bip)(NCCH₃) _n ](X)_2−m (X⁻ = NO₃ ⁻, CF₃SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N₄ tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH₃ versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO₃ ⁻ ≫ CF₃SO₃ ⁻ > ClO₄ ⁻ > BF₄ ⁻ ≫ PF₆ ⁻.     

A miniaturized active sampler for the assessment of personal exposure to nitrogen dioxide

A personalized, miniaturized air sampling system was evaluated to estimate the daily exposure of pediatric asthmatics to nitrogen dioxide (NO₂). The lightweight device (170 g) uses a sampling pump connected to a solid sorbent tube containing triethanolamine (TEA)-impregnated molecular sieve. The pump is powered by a 9 V battery and samples air over a 24 h period at a collection rate of 0.100 L/min. After exposure, the solid sorbent is removed from the tubes for spectrophotometric analysis (Griess Assay). The lower detection limit of the overall method for NO₂ is 11 μg/m³. The linearity, precision and accuracy of the sampler was evaluated. Different NO₂ concentrations generated in the laboratory (range: 50 to 340 μg/m³) were simultaneously measured by the TEA tube samplers and colocated continuous chemiluminescent NO_x analyzers (reference method). The coefficient of determination for the laboratory test derived from ordinary linear regression (OLR) was r ²=0.99 (y _OLR=0.94x−4.58) and the precision 3.6%. Further, ambient NO₂ concentrations in the field (range: 10–120 μg/m³) were verified with continuous chemiluminescent monitors next to the active samplers. Reweighted least squares analysis (RLS) based on the least median squares procedure (LMS) resulted in a correlation of r ²=0.68 for a field comparison in Riverside, CA (y _RLS=1.01x−0.94) and r ²=0.92 in Los Angeles, CA (y _RLS=1.31x−7.12). The precision of the TEA tube devices was 7.4% (at 20–60 μg/m³ NO₂) under outdoor conditions. Data show that the performance of this small active sampling system was satisfactory for measuring environmental concentrations of NO₂ under laboratory and field conditions. It is useful for personal monitoring of NO₂ in environmental epidemiology studies where daily measurements are desired.     

Effectiveness of nitric oxide ozonation

Attempts to develop new technologies of NO _x (NO + NO₂) emission reduction are still carried out all around the world. One of the relatively new approaches is the application of ozone injection into the exhaust gas stream followed by the absorption process. Ozone is used to transform NO _x to higher nitrogen oxides which yield nitric acid with better effectiveness. The main objective of this paper was to study the influence of mole ratio (MR) O₃/NO used in the ozonation process of NO _x on the effectiveness of NO _x oxidation to higher oxides. The ozonation process was carried out in a flow reactor for concentrations of nitric oxide in the range of 1.5 × 10⁻⁵−7.7 × 10⁻⁵ mol dm⁻³ and varying O₃/NO mole ratios. Measurements were conducted with the use of a FTIR spectrometer. The results obtained prove that for MR higher than 1, the oxidation effectiveness of nitric oxides generally reaches 95 %, whereas for MR higher than 2, oxidation of NO _x to higher nitrogen oxides is completed.     

N<Subscript>2</Subscript>O Production by Nitrifying Biomass Under Anoxic and Aerobic Conditions

The capacity of nitrifying biomass, grown in biofilms or in suspension, to reduce NO₂ ^- and NO₃ ⁻ under anoxic conditions was tested in batch experiments. The estimated reduction rates were 5 and 25 mg N per gram volatile suspended solids (VSS) per day for nitrate and nitrite, respectively, in the case of the nitrifying biofilms. Activity tests carried out with successive feedings indicated that no acclimation of the biomass to the tested conditions occurred, as the obtained reduction rates remained almost constant. Another series of activity assays was carried out with nitrifying suspended biomass, and the reduction rates for nitrate and nitrite were 30.4 and 48.9 mg N per gram VSS per day, respectively. N₂O and N₂ were the final gaseous products, and their percentages depended on the source of nitrogen feed. The specific production of nitrous oxide during nitrification was investigated during continuous experiments in a biofilm airlift suspension reactor. Specific production rates up to 46 mg N₂O–N per gram VSS per day were measured. The percentage of N₂O produced represented up to 34.4% of the ammonia oxidized. Nitrite accumulation, low dissolved oxygen concentrations, and the presence of organic matter favored the production of nitrous oxide. N₂O gas was not detected during the oxidation of nitrite even when organic matter was present. To prevent N₂O gas production in nitrifying systems, the operation at low dissolved oxygen concentrations, nitrite presence, or organic matter content should be avoided.     

Influence of ammonium on the performance of a denitrifying culture under heterotrophic conditions

The effect of ammonium on a denitrifying reactor of the upflow anaerobic sludge blanket type was studied. At a constant nitrate loading rate (2500 mg NO ₃ ⁻ -N/[L · d]), using acetate as organic electron donor and at a C/NO ₃ ⁻ -N ratio of 1.23, an increase in the N₂ production rate was observed when the ammonium loading rate was increased (25, 250, and 500 mg NH ₄ ⁺ -N/[L · d]). Dissimilatory nitrate reduction to ammonium (DNRA) was not observed, and the N₂ production efficiency was increased from 84 to 100% or higher. Since NH ₄ ⁺ in the output was lower than in the input, it was suggested that it was used for nitrate reduction. At constant NH ₄ ⁺ -N/NO ₃ ⁻ -N and C/NO ₃ ⁻ -N ratios of 0.2 and 1.63, respectively, the molecular nitrogen production rate was increased at 300 and 500 mg NH ₄ ⁺ -N/(L · d), whereas at 200 mg NH ₄ ⁺ -N/(L · d) DNRA took place probably owing to culture conditions of low reductive power. Molecular nitrogen production was not observed under autotrophic conditions, and the addition of acetate to the culture recovered its high nitrogen removal rate. Experimental results and balances indicated that the consumed ammonium was used as an additional reductive source.     

Anaerobic treatment of biodiesel by-products in a pilot scale reactor

In this work, long-term operation of a pilot scale mixed anaerobic reactor processing crude glycerol and rapeseed meal is discussed. These materials are generated as by-products of biodiesel production. Mixed reactor was operated under mesophilic conditions for the period of 654 days. Total cumulative production of biogas reached 379 m³ (at atmospheric pressure and ambient temperature). Maximum volumetric loading achieved during the operation was 2.17 kg m⁻³ d⁻¹ for the crude glycerol dose of 2 L. When dosing crude glycerol as a single substrate, average specific production of biogas of 0.76 m³ per L of the g-phase was achieved. The lack of nutrients in the g-phase had to be compensated by an addition of ammonium nitrogen in the form of urea into the reactor. Long term processing of crude glycerol demonstrated that accumulation of dissolved inorganic salts in the reactor can lead to inhibition of the methanogenic activity of microorganisms, causing breakdown of the system. Co-fermentation of crude glycerol with rapeseed meal provided stable biogas production and it was shown to be a feasible way of anaerobic degradation of these substrates. At the maximum volumetric load of 1.33 kg m⁻³ d⁻¹ (500 mL of g-phase and 500 g of rapeseed meal), the average biogas production reached 0.58 m³ d⁻¹.     

Monitoring of the <Superscript>14</Superscript>C concentration in the stack air of the nuclear power plant VVER Jaslovske Bohunice

¹⁴C releases in the stack air of the NPPs V1 and V2, Jaslovske Bohunice was determined during the year 2004–2010. Radioactivity concentration of ¹⁴C in the stack air was determined in the forms of inorganic ¹⁴CO₂ and ¹⁴C _n H _m . The annual average activity concentration in the stacks air samples varies between 12 and 121 Bq m⁻³. NPP V1, starting with 45 Bq m⁻³ in 2005 is decreasing due to the shutting down of the reactors (the first reactor was shut down in December 2006 and the second reactor in December 2008). The average value of radioactivity concentration for power unit V2 was 32 Bq m⁻³ in 2004 and reached the value of 102 Bq m⁻³ in the first-quarter of the 2010. The average normalized yearly discharge rates were between 0.39 and 0.64 TBq GW_e⁻¹ year⁻¹ (2005–2008), NPP V1 and 0.19–0.61 TBq GW_e⁻¹ year⁻¹ (2004–first-quarter 2010) for NPP V2, Jaslovske Bohunice. Most of the discharged ¹⁴C is in a hydrocarbon form, (95% for Jaslovske Bohunice NPP V2), but the CO₂ fraction may reach 37% in the air stack for Jaslovske Bohunice V1.     

The Stability of Accumulating Nitrite from Swine Wastewater in a Sequencing Batch Reactor

Shortcut nitrification is the first step of shortcut nitrogen removal from swine wastewater. Stably obtaining an effluent with a significant amount of nitrite is the premise for the subsequent shortcut denitrification. In this paper, the stability of nitrite accumulation was investigated using a 1.5-day hydraulic retention time in a 10-L (working volume) activated sludge sequencing batch reactor (SBR) with an 8-h cycle consisted of 4 h 38 min aerobic feeding, 1 h 22 min aerobic reaction, 30 min settling, 24 min withdrawal, and 1 h 6 min idle. The nitrite production stability was tested using four different ammonium loading rates, 0.075, 0.062, 0.053, and 0.039 g NH₄-N/g (mixed liquid suspended solid, MLSS) day in a 2-month running period. The total inorganic nitrogen composition in the effluent was not affected when the ammonium load was between 0.053 and 0.075 g NH₄-N/g MLSS · day (64% NO₂-N, 16% NO₃-N, and 20% NH₄-N). Under 0.039 g NH₄-N/g MLSS · day, more NO₂-N was transformed to NO₃-N with an effluent of 60% NO₂-N, 20% NO₃-N, and 20% NH₄-N. The reducing load test was able to show the relationship between a declining free nitrous acid (FNA) concentration and the decreasing nitrite production, indicating that the inhibition of FNA on nitrite oxidizing bacteria depends on its levels and an ammonium loading rate around 0.035 g NH₄-N/g MLSS · day is the lower threshold for producing a nitrite dominance effluent in the activated sludge SBR under the current settings.     

Evaluation of Multiple Corona Reactor Modes and the Application in Odor Removal

Effects of multiple corona reactor modes on pulse characteristics, energy transfer efficiency, and odor (H₂S and NH₃) removal were investigated experimentally by the wire-plate corona reactor(s). The removal efficiency of H₂S was only 91% and the energy consumption was 16.1 Wh m⁻³ by the single mode with a gas-flow rate of 23 m³ h⁻¹ and an initial concentration of 200 mg m⁻³. At the same experimental conditions, almost 100% removal efficiency was achieved and the energy consumption was only 12.8 and 14.9 Wh m⁻³ by the series and parallel modes. In the case of 50 mg m⁻³ NH₃ removal at the same gas-flow rate, the removal efficiencies with the single mode, the series and parallel modes were 64, 92 and 70%, respectively. The energy requirement did not increase at the same residence time under the experimental conditions of the single mode with a gas-flow rate of 11.5 m³ h⁻¹ and the series or parallel mode with a gas-flow rate of 23.0 m³ h⁻¹. The experimental results indicate that the series and parallel modes are effective in saving energy consumption, improving removal ability and efficiency, especially for the series mode.     

Computational study on the reaction mechanism of the gas-phase atom-negative ion of S?+?NO2 ?: comparative study of mechanism with S?+?O3 reaction as isoelectronic and isostructure systems

The reaction mechanism of sulfur vapor (S) with nitrite ion (NO₂ ⁻) has been investigated theoretically on the triplet and singlet potential energy surfaces (PESs). All stationary points for the title reaction have been optimized at the B3LYP/6-311+G(3df) level. The energetic data have been obtained at the CCSD(T)//B3LYP level employing the 6-311+G(3df) basis set. Five stable collision complexes, ³IN1 (S–ONO⁻), ³IN2 (cyclic SONO⁻), ¹IN1 (cis S–ONO⁻), ¹IN2 (S–NO₂ ⁻), and ¹IN3 (trans S–ONO⁻), have been considered on the triplet and singlet PESs through barrier-less and exothermic processes. By starting from these complexes, a simple mechanism has been obtained on the triplet PES while a complex mechanism has been considered on the singlet PES. The calculated results show that there are no favorable paths for the reaction of S with NO₂ ⁻ on the singlet PES. Therefore, the S + NO₂ ⁻ reaction proceeds only on the triplet PES to produce ³SO + ³NO⁻ as main products. The results from the comparative study of S + NO₂ ⁻ reaction mechanism with S + O₃ (as isoelectronic and isostructure reactions) on the singlet PES show similarities in the overall trend of reaction mechanism and atom connectivity and differences in the stability of intermediates and the energy barriers of transition states.     

Heat Capacities and Thermodynamic Properties of a H2O + Li2B4O7 Solution in the Temperature Range from 80 to 356 K

The molar heat capacities of an aqueous Li₂B₄O₇ solution were measured with a precision automated adiabatic calorimeter in the temperature range from 80 to 356 K at a concentration of 0.3492 mol⋅kg⁻¹. The occurrence of a phase transition was determined based on the changes in the curve of the heat capacity with temperature. A phase transition was observed at 271.72 K corresponding to the solid-liquid phase transition; the enthalpy and entropy of the phase transition were evaluated to be Δ H _m = 4.110 kJ⋅mol⁻¹ and Δ S _m = 15.13 J⋅K⁻¹⋅mol⁻¹, respectively. Using polynomial equations and thermodynamic relationship, the thermodynamic functions [H _T −H _298.15] and [S _T −S _298.15] of the aqueous Li₂B₄O₇ solution relative to 298.15 K were calculated in temperature range 80 to 355 K at intervals of 5 K. Values of the relative apparent molar heat capacities of the aqueous Li₂B₄O₇ solution, C _p,φ, were calculated at every 5 K in temperature range from 80 to 355 K from the experimental heat capacities of the solution and the heat capacities of pure water.     

Osmotic Coefficients of the Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript>+LiCl + H<Subscript>2</Subscript>O System at <Emphasis Type="Italic">T</Emphasis>=273.15 K

Osmotic coefficients and water activities for the Li₂B₄O₇+LiCl+H₂O system have been measured at T=273.15 K by the isopiestic method, using an improved apparatus. Two types of osmotic coefficients, φ _S and φ _E, were determined. φ _S is based on the stoichiometric molalities of the solute Li₂B₄O₇(aq), and φ _E is based on equilibrium molalities from consideration of the equilibrium speciation into H₃BO₃,B(OH)₄⁻ and B₃O₃(OH)₄⁻. The stoichiometric equilibrium constants K _m for the aqueous speciation reactions were estimated. Two types of representations of the osmotic coefficients for the Li₂B₄O₇+LiCl+H₂O system are presented with ion-interaction models based on Pitzer’s equations with minor modifications: model (I) represents the φ _S data with six parameters based on considering the ion-interactions between three ionic species of Li⁺, Cl⁻, and B₄O₇²⁻, and model (II) for represents the φ _E data based on considering the equilibrium speciation. The parameters of models (I) and (II) are presented. The standard deviations for the two models are 0.0152 and 0.0298, respectively. Model (I) was more satisfactory than model (II) for representing the isopiestic data.     

Kinetics of thermal decomposition of dinitramide

Kinetic regularities of thermal decomposition of dinitramide in aqueous and sulfuric acid solutions were studied in a wide temperature range. The rate of the thermal decomposition of dinitramide was established to be determined by the rates of decomposition of different forms of dinitramide as the acidity of the medium increases: first, N(NO₂)⁻ anions, then HN(NO₂)₂ molecules, and finally, protonated H₂N(NO₂)₂ ⁺ cations. The temperature dependences of the rate constants of the decomposition of N(NO₂)⁻ (k _an) and HN(NO₂)₂ (k′_ac) and the equilibrium constant of dissociation of HN(NO₂)₂ (K _a) were determined:k _an=1.7·10¹⁷ exp(−20.5·10³/T), s⁻¹,k′_ac=7.9·10¹⁶ exp(−16.1·10³/T), s⁻¹, andK _a=1.4·10 exp(−2.6·10³/T). The temperature dependences of the decomposition rate constant of H₂N(NO₂)₂ ⁺ (k _d) and the equilibrium constant of the dissociation of H₂N(NO₂)₂ ⁺ (K _d) were estimated:k _d=10¹² exp(−7.9·10³/T), s⁻¹ andK _d=1.1 exp(6.4·10³/T). The kinetic and thermodynamic constants obtained make it possible to calculate the decomposition rate of dinitramide solutions in a wide range of temperatures and acidities of the medium. In this series of articles, we report the results of studies of the thermal decomposition of dinitramide performed in 1974–1978 and not published previously. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2129–2133, December, 1997.