Alternate Solvents

Chemical reactions are diverse and are known to occur at a wide range of temperature and pressure conditions. In most reactions, the reaction vessel provides the following three components (see Fig. 5.1)  

Since chemical systems are irreversible, nonequilibrium systems, they can be labeled chaotic. Hence, they may be viewed as macroscopic analogues to the quantum uncertainties. Just as in a chaotic system, every component—minor or major—affects the outcome of the change or transformation, every component affects the outcome of the reaction. 

---

Carbon disulphide should never be used if any alternative solvent is available, as it has a dangerously low flash-point, and its vapours form exceedingly explosive mixtures with air. Ether as a solvent for recrystallisation is much safer than carbon disulphide, but again should be avoided whenever possible, partly on account of the danger of fires, and partly because the filtered solution tends to creep up the walls of the containing vessel and there deposit solid matter by complete evaporation instead of preferential crystallisation. 

Hydrochloric acid digestion takes place at elevated temperatures and produces a solution of the mixed chlorides of cesium, aluminum, and other alkah metals separated from the sUiceous residue by filtration. The impure cesium chloride can be purified as cesium chloride double salts such as cesium antimony chloride [14590-08-0] 4CsCl SbCl, cesium iodine chloride [15605 2-2], CS2CI2I, or cesium hexachlorocerate [19153 4-7] Cs2[CeClg] (26). Such salts are recrystaUized and the purified double salts decomposed to cesium chloride by hydrolysis, or precipitated with hydrogen sulfide. Alternatively, solvent extraction of cesium chloride direct from the hydrochloric acid leach Hquor can be used. 

For worker exposure to trichloroethylene vapor, OSHA set a maximum eight-hour time-weighted average (TWA) concentration of 100 ppm. This severely restricted certain appHcations, and many organizations converted to other chlorinated solvents. As a result, U.S. production of trichloroethylene declined about 70% from a peak in 1970 (Table 2). In 1989, OSHA lowered the permissible exposure limit (PEL) from 100 ppm eight-hour TWA to 50 ppm eight-hour TWA (33). This added further pressure for some users to consider changing to alternative solvents. 

Ethylene Oxide Recovery. An economic recovery scheme for a gas stream that contains less than 3 mol % ethylene oxide (EO) must be designed. It is necessary to achieve nearly complete removal siace any ethylene oxide recycled to the reactor would be combusted or poison the carbon dioxide removal solution. Commercial designs use a water absorber foUowed by vacuum or low pressure stripping of EO to minimize oxide hydrolysis. Several patents have proposed improvements to the basic recovery scheme (176—189). Other references describe how to improve the scmbbiag efficiency of water or propose alternative solvents (180,181). 

Hot feed Provide and maintain an automated inerting (increases system—oxygen concentration or pressure fire/explosion risk controlled with flammable. Eliminate leakage sources (ftimes/air) solvents). Use alternative solvents (nonflammable or less flammable) Reduce feed temperature and/or monitor temperature of feed and interlock with feed shutdown NFPA 69... 

Use alternate solvent with reduced static potential Use conductive materials of construction Add antistatic agent to nonpolar solvent Check conductivity prior to feeding Use static dissipating linings if applicable... 

Benzene, which has been used as a solvent successfully and extensively in the past for reactions and purification by chromatography and crystallisation is now considered a very dangerous substance so it hasto be used with extreme care. We emphasise that an alternative solvent system to benzene (e.g. toluene, toluene-petroleum ether, or a petroleum ether to name a few) should be used first. However, if no other solvent system can be found then all operations involving benzene have to be performed in an efficient fumehood and precautions must be taken to avoid inhalation and contact with skin and eyes. Whenever benzene is mentioned in the text an asterisk e.g. C Hg or benzene, is inserted to remind the user that special precaution should be adopted. 

A solvent used in an exothermic reaction is nonvolatile, and moderately toxic. An alternative solvent is less toxic, but also has a much lower boiling point. There is a trade-off between toxic hazards and the potential for tempering the exotherm, but also generating pressure from boiling solvent in case of a runaway reaction. 

In many cases, it is possible to replace environmentally hazardous chemicals with more benign species without compromising the technical and economic performance of the process. Examples include alternative solvents, polymers, and refrigerants. Group contribution methods have been conunonly used in predicting physical and chemical properties of synthesized materials. Two main frameworks have... 

Inhibited THF is problematic for semipreparative separations. Because small quantities of polymer are being collected along with larger volumes of solvent, more inhibitor, usually butylated hydroxytoluene (BHT), than sample is often collected in each fraction. Thus, one must carefully consider if the BHT will cause a problem in the subsequent analysis of the isolated fractions. If it does, uninhibited THF or other alternate solvents should be used. It must be remember that if uninhibited THF is used, the analyst must pay careful attention to the inevitable peroxide formation in the solvent/fractions. 

As already noted (p. 1073), the platinum metals are all isolated from concentrates obtained as anode slimes or converter matte. In the classical process, after ruthenium and osmium have been removed, excess oxidants are removed by boiling, iridium is precipitated as (NH4)2lrCl6 and rhodium as [Rh(NH3)5Cl]Cl2. In alternative solvent extraction processes (p. 1147) [IrClg] " is extracted in organic amines leaving rhodium in the aqueous phase to be precipitated, again, as [Rh(NH3)5Cl]Cl2. In all cases ignition in H2... 

Obviously, there are many good reasons to study ionic liquids as alternative solvents in transition metal-catalyzed reactions. Besides the engineering advantage of their nonvolatile natures, the investigation of new biphasic reactions with an ionic catalyst phase is of special interest. The possibility of adjusting solubility properties by different cation/anion combinations permits systematic optimization of the biphasic reaction (with regard, for example, to product selectivity). Attractive options to improve selectivity in multiphase reactions derive from the preferential solubility of only one reactant in the catalyst solvent or from the in situ extraction of reaction intermediates from the catalyst layer. Moreover, the application of an ionic liquid catalyst layer permits a biphasic reaction mode in many cases where this would not be possible with water or polar organic solvents (due to incompatibility with the catalyst or problems with substrate solubility, for example). 

To overcome these limitations, there has been a great deal of investigation of novel methods, one of them focused on the search for alternative solvents [6, 7]. Table 5.3-1 gives different approaches to biphasic catalysis, with some of their respective advantages and limitations. 

The epoxy-acrylic resin referred to above is a graft copolymer prepared by the polymerisation of acrylic monomers in the presence of the epoxy resin in such a way that grafting of the acrylic onto the epoxy takes place. Water dispersibility is achieved by neutralising carboxyl groups in the acrylic polymer chain with ammonia or amine. Amino or phenolic resins are used as crosslinkers. Alternatively, solvent-borne epoxy-amino or epoxy-phenolic lacquers can be used. 

As outlined above, immobilization in a fluorinated liquid phase demands the functionahzation of the ligand with perfluoroalkyl chains and, even then, the solubihty is strongly influenced by the nature of the complex. Ionic hquids of the alkylmethyhmidazolium type (Fig. 4) have been recently developed as alternative solvents for organometallic catalysis and have the practical advantage of using directly the commercially available chiral hgands and complexes. 

Alternative solvents were also tested. Isopropanol and methyl tertiary-butyl ether (MTBE) with water (HCl), the latter a two-phase system, the displayed reaction rates were much slower. 

For selection of alternative solvents (non-ozone depleting) for separation processes (extraction and HPLC mobile phase optimisation) references [24,25] are very useful. 

Significant progress has been made in the application of ionic liquids (ILs) as alternative solvents to C02 capture because of their unique properties such as very low vapour pressure, a broad range of liquid temperatures, excellent thermal and chemical stabilities and selective dissolution of certain organic and inorganic materials. ILs are liquid organic salts at ambient conditions with a cationic part and an anionic part. 

To effect reduction to the parent heterocycle, a solution of the dichloro compound in DMF was being added to a hot solution of sodium tetrahydroborate in the same solvent, when a violent explosion occurred [1,2]. This may have arisen either from interaction of the dichloro compound with the solvent, or from the known instability of hot solutions of the tetrahydroborate in DMF. Use of aqueous diglyme as an alternative solvent [3] would only be applicable to this and other hydrolytically stable halides [2],... 

Compared to the inexpensive and ubiquitous solvent and support, water, with its unique combination of properties, other alternative solvents may well remain unimportant. Others make the same comments using different words (Table 5.2). 

There are many good reasons for applying ionic liquids as alternative solvents in transition metal catalysed reactions. Besides their very low vapour pressure and then-good thermal stability [33], an important advantage is the possibility of tuning then-solubility [34] and acidity/coordination properties [35] by varying the nature of the anions and cations systematically. 

Discuss possible process alternatives and their relative hazards, including discussions on such topics as alternative solvents and possible incompatibilities to avoid. 

As an aside, benzotrifluoride is a slightly polar, non-Lewis basic solvent that has favorable properties for many kinds of organic reactions. A. Ogawa, D. P. Curran, Benzotrifluoride A useful alternative solvent for organic reactions currently conducted in dichloro-methane and related solvents , J. Org Chem. 1997, 62, 450. 

---