Solvents ammonia, supercritical

Supercritical Fluid Chromatography. Supercritical fluid chromatography (sfc) combines the advantages of gc and hplc in that it allows the use of gc-type detectors when supercritical fluids are used instead of the solvents normally used in hplc. Carbon dioxide, -petane, and ammonia are common supercritical fluids (qv). For example, carbon dioxide (qv) employed at 7.38 MPa (72.9 atm) and 31.3°C has a density of 448 g/mL. 

Supercritical fluid solvents have been tested for reactive extractions of liquid and gaseous fuels from heavy oils, coal, oil shale, and biomass. In some cases the solvent participates in the reactions, as in the hydrolysis of coal and heavy oils with water. Related applications include conversion of cellulose to glucose in water, dehgnincation of wood with ammonia, and liquefaction of lignin in water. 

Scheme 12 Synthesis of metal polysulfido complexes using supercritical ammonia as a solvent...

The first use of supercritical fluid extraction (SFE) as an extraction technique was reported by Zosel [379]. Since then there have been many reports on the use of SFE to extract PCBs, phenols, PAHs, and other organic compounds from particulate matter, soils and sediments [362, 363, 380-389]. The attraction of SFE as an extraction technique is directly related to the unique properties of the supercritical fluid [390]. Supercritical fluids, which have been used, have low viscosities, high diffusion coefficients, and low flammabilities, which are all clearly superior to the organic solvents normally used. Carbon dioxide (C02, [362,363]) is the most common supercritical fluid used for SFE, since it is inexpensive and has a low critical temperature (31.3 °C) and pressure (72.2 bar). Other less commonly used fluids include nitrous oxide (N20), ammonia, fluoro-form, methane, pentane, methanol, ethanol, sulfur hexafluoride (SF6), and dichlorofluoromethane [362, 363, 391]. Most of these fluids are clearly less attractive as solvents in terms of toxicity or as environmentally benign chemicals. Commercial SFE systems are available, but some workers have also made inexpensive modular systems [390]. 

Liquefied or Supercritical Cases as Solvents for Electrolytes For very special applications, where the increased efforts for low temperature and/or pressurized cells are acceptable, liquefied gases, for example, sulfur dioxide or ammonia, can be interesting solvents for electrolytes (see e.g. [3a]). Supercritical fluids show remarkable properties that are very different from other solvents. Detrimental to electrochemistry is that especially the dielectric constant in the supercritical state becomes low. For supercritical carbon dioxide, no supporting electrolyte with sufficient conductivity is known. 

The single largest use of ammonia is its direct apphcation as fertdizer, and in the manufacture of ammonium fertilizers that have increased world food production dramatically. Such ammonia-based fertilizers are now the primary source of nitrogen in farm soils. Ammonia also is used in the manufacture of nitric acid, synthetic fibers, plastics, explosives and miscellaneous ammonium salts. Liquid ammonia is used as a solvent for many inorganic reactions in non-aqueous phase. Other apphcations include synthesis of amines and imines as a fluid for supercritical fluid extraction and chromatography and as a reference standard in i N-NMR. 

In 1981, Silvestri et al. [23] used supercritical HC1 and NH3 for studying the anodic dissolution of Fe and Ag. Since then, electrochemical studies in SCF solvents have been carried out to a considerable extent. Bard and his coworkers [24] carried out in supercritical water, ammonia, and acetonitrile a series of studies... 

From standard literature references, find the critical pressure and temperatures of methane, methyl amine (CH3NH2), ammonia, and tetrafluoromethane. Discuss the suitability of using each of these solvents for a supercritical extraction at room temperature inside an autoclave, which can withstand pressures of up to 100 atm. 

A test was made with 2-methylpentane as the supercritical solvent at 514 K and 4.37 MPa, at a molecular sieve to oil ratio of 5.85 and a solvent to oil ratio of 20.1. The n-paraffin content of the wax distillate was reduced by 77% to a level of 3.8 wt %. In this test, an extraordinary gain in molecular sieve weight occurred. A significant amount of the 2-methylpentane was recovered upon desorption of the molecular sieves with ammonia. 

Absorption spectra of 2-nitroanisole in supercritical C02, N20, Freon-13, ammonia and C02-methanol mixtures were obtained on a Cary model 1605 spectrophotometer operated in the dual beam mode. The gases used as supercritical solvents were of the highest purity available from the supplier (Matheson) and were further filtered prior to use. The mixed solvent system of C02-methanol was obtained from Scott Speciality Gases (15.4 wt% methanol), and other mixtures were made in the laboratory. Spectra of 2-nitroanisole in n-pentane, methanol, tetrahydrofuran and acetonitrile (Burdick A Jackson) were obtained using quartz cells with a 1-cm light path and with a pure solvent blank in the reference beam. Vapor phase and supercritical fluid spectra were obtained using an air reference. 

Liquid ammonia has been suggested as a solvent for the C4 separation(l). A drawback to its use in the liquid state, however, is the need for costly refrigeration. Its use as a supercritical solvent would also be acceptable were it not for its high critical temperature (405.45 K). High temperature favors the polymerization of the butadiene hence, its limitation in this role. In this study, a method was developed that seeks to circumvent this problem and yet achieve the desired separation of the C4 s. Prausnitz(2) discusses the use of a mixture of supercritical solvents whose properties provide the optimal physical conditions for efficient extraction. It is equally possible to prepare mixtures of solvents that not only modify those critical properties of the individual solvent component, but also introduce the chemical features needed to maximize the separation of the feed mixture. 

We have applied some of these principles to the extraction of 1-butene from a binary mixture of 1,3-butadiene/1-butene. Various mixtures of sc solvents (e.g., ethane, carbon dioxide, ethylene) are used in combination with a strongly polar solvent gas like ammonia. The physical properties of these components are shown in Table I. The experimental results were then compared with VLE predictions using a newly developed equation of state (18). The key feature of this equation is a new set of mixing rules based on statistical mechanical arguments. We have been able to demonstrate its agreement with a number of binary and ternary systems described in the literature, containing various hydrocarbon compounds, a number of selected polar compounds and a supercritical component. 

This study is by no means comprehensive and covers only a narrow range of variables. However, it does demonstrate the influence of entrainer in the improvement of separation over a single supercritical solvent. The increase in selectivity (1.4 to 1.8) for butene/butadiene mixtures is compared with the value of 1.63 obtained with liquid ammonia for the same binary system(l). Moreover, it has been demonstrated that a mixture of a pure solvent and an entrainer permits an improvement in the separation at temperatures and pressures lower than would have been otherwise predicted with a single gas solvent(20). For mixtures containing a highly polar component, such as ammonia, molecular size alone cannot account for the large selectivities observed in these experiments. At present, all theories are inadequate in explaining the chemical interactions between the entrainer and the mixture. The state of the art is comparable to liquid phase solvent extraction. 

The separation of the liquid components in the presence of a supercritical solvent occurs much as it does in liquid extraction with the entrainer, ammonia, concentrating in the liquid to increase the relative volatility of the butene to butadiene. The butadiene migrates to the ammonia-rich phase while the solvent gas phase or "vapor" will contain the butene. 

The explanation for the higher selectivity of the ethylene/ ammonia mixture over the ethane/ammonia system is somewhat surprising. The efficiency of sc extraction of a given solvent toward a particular solute is related to the supercritical... 

Furthermore, life should be considered possible in aqueous environments that are extreme in their solute content, in their acidity or alkalinity, and in their temperature range, especially with ammonia as an antifreeze in low-temperature water-ammonia eutectics. The committee sees no reason to exclude the possibility of life in environments as diverse as the aerosols above Venus and the water-ammonia eutectics of Titan. It seems that life is less likely in more exotic solvents—such as liquid dinitrogen, liquid methane, and supercritical dihydrogen—but this conclusion is based on few data. 

A solvothermal process is one in which a material is either recrystallized or chemically synthesized from solution in a sealed container above ambient temperature and pressure. The recrystallization process was discussed in Section 1.5.1. In the present chapter we consider synthesis. The first solvothermal syntheses were carried out by Robert Wilhelm Bunsen (1811-1899) in 1839 at the University of Marburg. Bunsen grew barium carbonate and strontium carbonate at temperatures above 200°C and pressures above 100 bar (Laudise, 1987). In 1845, C. E. Shafhautl observed tiny quartz crystals upon transformation of freshly precipitated silicic acid in a Papin s digester or pressure cooker (Rabenau, 1985). Often, the name solvothermal is replaced with a term to more closely refer to the solvent used. For example, solvothermal becomes hydrothermal if an aqueous solution is used as the solvent, or ammothermal if ammonia is used. In extreme cases, solvothermal synthesis takes place at or over the supercritical point of the solvent. But in most cases, the pressures and temperatures are in the subcritical realm, where the physical properties of the solvent (e.g., density, viscosity, dielectric constant) can be controlled as a function of temperature and pressure. By far, most syntheses have taken place in the subcritical realm of water. Therefore, we focus our discussion of the materials synthesis on the hydrothermal process. 

In this chapter, we have reviewed some of our own work on solvation properties in supercritical fluids using molecular dynamics computer simulations. We have presented the main aspects associated with the solvation structures of purine alkaloids in CO2 under different supercritical conditions and in the presence of ethanol as co-solvent, highlighting the phenomena of solvent density augmentation in the immediate neighborhood of the solute and the effects from the strong preferential solvation by the polar co-solvent. We have also presented a summary of our results for the structure and dynamics of supercritical water and ammonia, focusing on the dielectric behavior of supercritical water as functions of density and temperature and the behavior of excess solvated electrons in aqueous and non-aqueous associative environments. 

Potentially, supercritical carbon dioxide (SCCO2) is the ideal green solvent. It is non-toxic for both humans and the environment. It is chemically inert under most conditions, whether they be non-flammable or non-protic, and it is inert to radical and oxidizing conditions. This gas can be obtained in large quantities as a by-product of fermentation, combustion, and ammonia synthesis and it is relatively cheap, particularly compared with conventional solvents. Supercritical carbon dioxide presents other practical advantages as well, such as the possibility of achieving product isolation to total dryness by simple evaporation. 

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