Nitrate phase

FIG. 5.4 The potassium nitrate /sulfur /aluminum system. Endo-therms for sulfur can be seen near 105° and 119 c, followed by the potassium nitrate phase transition near 130 C. As the melting point of potassium nitrate is approached (334 C), an exotherm is observed. A reaction has occurred between the oxidizer and fuel, and ignition of the mixture evolves a substantial amount of heat. 

Figure 2.29 Scanning electron micrographs at approximately the same magnification of four microporous membranes having approximately the same particle retention, (a) Nuclepore (polycarbonate) nucleation track membrane (b) Celgard (polyethylene) expanded film membrane (c) Millipore cellulose acetate/cellulose nitrate phase separation membrane made by water vapor imbibition (Courtesy of Millipore Corporation, Billerica, MA) (d) anisotropic polysulfone membrane made by the Loeb-Sourirajan phase separation process...

The first major application of microfiltration membranes was for biological testing of water. This remains an important laboratory application in microbiology and biotechnology. For these applications the early cellulose acetate/cellulose nitrate phase separation membranes made by vapor-phase precipitation with water are still widely used. In the early 1960s and 1970s, a number of other membrane materials with improved mechanical properties and chemical stability were developed. These include polyacrylonitrile-poly(vinyl chloride) copolymers, poly(vinylidene fluoride), polysulfone, cellulose triacetate, and various nylons. Most cartridge filters use these membranes. More recently poly(tetrafluo-roethylene) membranes have come into use. 

This intermolecular potential for ADN ionic crystal has further been developed to describe the lowest phase of ammonium nitrate (phase V) [150]. The intermolecular potential contains similar potential terms as for the ADN crystal. This potential was extended to include intramolecular potential terms for bond stretches, bond bending and torsional motions. The corresponding set of force constants used in the intramolecular part of the potential was parameterized based on the ab initio calculated vibrational frequencies of the isolated ammonium and nitrate ions. The temperature dependence of the structural parameters indicate that experimental unit cell dimensions can be well reproduced, with little translational and rotational disorder of the ions in the crystal over the temperature range 4.2-250 K. Moreover, the anisotropic expansion of the lattice dimensions, predominantly along a and b axes were also found in agreement with experimental data. These were interpreted as being due to the out-of-plane motions of the nitrate ions which are positions perpendicular on both these axes. 

Chasan, D. E. and Norwitz, G., Applications of Spectroscopy to the Analysis of Inorganic Nitrates Phase II. Test Rept. T-69-3-1, Dept, of the Army, Frankford Arsenal, March 1969. 

It is to be noted that the ion interaction coefficients for Th" and discussed above refer to a strict ion interaction approach which does not account for the formation of chloride and nitrate complexes. This review has re-evaluated the Th(lV) extraction data from aqueons nitrate phases using also the complexation model. Figure A-52 shows that the experimental data of [2006NEC/ALT] in 0.05-3 M NaNOs + 0.02 M HNO3 can be described eqnally well with both approaches. 

Fluid-fluid systems are widely used in chemical, petroleum, pharmaceutical, hydrometaflurgical, and food industries. Commercially important examples of gas-liquid mass transfer with or without reaction include gas purification, oxidation, halogenations, hydrogenation, and hydroformylation to name but a few. Important liquid-liquid reactions include nitration, phase transfer catalysis (PTC), cyclization, emulsion polymerization, homogenous catalyst screening, enzymatic reactions, extraction, precipitation, crystallization, and cell separation. 

However, in the HDEHP (toluene) vs. HX system it was found, in gross experiments, that nitrate was extracted, the ratio of nitrate to Th in the extractant phase approximating unity. This is consistent with the observation that tracer level Th" " is extracted with a far higher K from a nitrate phase than from a chloride or perchlorate phase. 

Granule structure formation by isothermal coarsening of dendilttc ammonium nitrate phase II, In Industrial Crystallization 93, VoL I (ed. RoJkowskI, Z.). p. 3-117, Warsaw 1993... 

The simpler nitrop>arafIins (nitromethane, nitroethane, 1- and 2-nitroproj)ane) are now cheap commercial products. They are obtained by the vapour phase nitration of the hydrocarbons a gaseous mixture of two mols of hydrocarbon and 1 mol of nitric acid vapour is passed through a narrow reaction tube at 420-476°. Thus with methane at 476° a 13 per cent, conversion into nitro methane is obtained ethane at 420° gives a 9 1 mixture of nitroethane (b.p. 114°) and nitromethane (b.p. 102°) propane at 420° afifords a 21 per cent, yield of a complex mixture of 1- (b.p. 130-6°) and 2-nitropropane (b.p. 120°), nitroethane and nitromethane, which are separated by fractional distillation. 

Particles are the major cause of the ha2e and the brown color that is often associated with smog. The three most important types of particles produced in smog are composed of organics, sulfates, and nitrates. Organic particles are formed when large VOC molecules, especially aromatics and cycHc alkenes, react with each other and form condensable products. Sulfate particles are formed by a series of reactions initiated by the attack of OH on SO2 in the gas phase or by Hquid-phase reactions. Nitrate particles are formed by... 

L. Asaoka, Phase Stabili d Ammonium Nitrate Effects on Minimum Signature Propellant Properties, Vol. 5, 3 CPIA Pubhcation 550, Anaheim, Calif., 1990. 

Many industrial processes involve a chemical reaction between two Hquid phases, for example nitration (qv), sulfonation (see Sulfonation and sulfation), alkylation (qv), and saponification. These processes are not always considered to be extractions because the main objective is a new chemical product, rather than separation (30). However these processes have many features in common with extraction, for example the need to maintain a high interfacial area with the aid of agitation and the importance of efficient phase separation after the reaction is completed. 

TBP and nitric acid also tend to form a complex with each other, but at sufftcientiy high uranyl nitrate concentrations the nitric acid is mainly displaced into the aqueous phase. 

Hitec Heat-Transfer Salt. Hitec heat-transfer salt, manufactured by Coastal Chemical Co., is an eutectic mixture of water-soluble inorganic salts potassium nitrate (53%), sodium nitrite (40%), and sodium nitrate (7%). It is suitable for Hquid-phase heat transfer at temperatures of 150—540°C. 

Therefore the extent of extraction or back-extraction is governed by the concentration of X ia the aqueous phase, the distribution coefficients, and selectivities depending on the anion. In nitrate solutions, the distribution coefficient decreases as the atomic number of the REE increases, whereas ia thiocyanate solutions, the distribution coefficient roughly increases as the atomic number of the REE increases. The position of yttrium in the lanthanide series is not the same in nitrate and thiocyanate solutions, and this phenomenon has been used for high purity yttrium manufacture in the past. A combination of extraction by carboxyUc acids then by ammonium salts is also utilized for production of high purity yttrium. 

Anhydrous magnesium nitrate [10377-60-3] Mg(N02)2, is very difficult to isolate. The commercial product is the deUquescent hexahydrate [13446-18-9] Mg(N02)2 6H20. As illustrated in the solubiUty curve in Figure 7, the hexahydrate is the stable soHd phase between —18 and 55—56°C. Properties are given in Table 17 (1 4). The unit ceU contains two formula units and the calculated density is 1.643 g/cm. ... 

Most ionic nitrations are performed at 0—120°C. For nitrations of most aromatics, there are two Hquid phases an organic and an acid phase. Sufficient pressure, usually slightly above atmospheric, is provided to maintain the Hquid phases. A large interfacial area between the two phases is needed to expedite transfer of the reactants to the interface and of the products from the interface. The site of the main reactions is often at or close to the interface (2). To provide large interfacial areas, a mechanical agitator is frequently used. 

Acetic anhydride and acetic acid increase the solubiUty of the two phases in each other, and they are employed for the commercial N-nitration of hexamethylenetetramine [100-97-0] (11) to form cyclotrimethylenetrinitramine [121-82-4] (RDX), (CH2)3(NN02)3. Renewed consideration has been given to replacing H2SO4 with an improved soHd catalyst to reduce the environmental problems of disposal or reconcentration of the waste acid and to increase production of desired nitrated isomers. For example, a catalyst with suitable pore size might increase the production of 4-MNT and reduce that of 3-MNT when toluene is nitrated. 

Zeohtes have recendy been employed as soHd catalysts for the vapor-phase nitration of aromatics with nitric acid. Additional research is required to improve yields and to niinimi2e loss of catalytic activity as the nitration progresses (see Molecularsieves). 

Rates of nitration determined over a range of temperatures in two-phase dispersions have been used to calculate energies of activation from 59—75 kj/mol (14—18 kcal/mol). Such energies of activation must be considered as only apparent, since the tme kinetic rate constants, NO2 concentrations, and interfacial area all change as temperature is increased. 

Increased agitation of a given acid—hydrocarbon dispersion results in an increase in interfacial areas owing to a decrease in the average diameter of the dispersed droplets. In addition, the diameters of the droplets also decrease to relatively low and nearly constant values as the volume % acid in the dispersions approaches either 0 or 100%. As the droplets decrease in si2e, the ease of separation of the two phases, following completion of nitration, also decreases. 

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