Liquid reagent systems

The advantage of dry chemistry technology is that it eliminates the need for reagent preparation and many other manual steps common to liquid reagent systems, resulting in greater consistency and reliability of test results. Each test unit contains all the reagents and reactants necessary to perform analyses. 

Figure 14-10 illustrates the gas-film and liquid-film concentration profiles one might find in an extremely fast (gas-phase mass-transfer limited) second-order irreversible reaction system. The solid curve for reagent B represents the case in which there is a large excess of bulk-liquid reagent B. The dashed curve in Fig. 14-10 represents the case in which the bulk concentration B is not sufficiently large to prevent the depletion of B near the liquid interface and for which the equation ( ) = I -t- B /vCj is applicable. 

Pressure measurement deviees sueh as a manometer are used without disturbing the system being monitored. Another type of reaeting system that ean be monitored involves one of the produets being quantitatively removed by a solid or liquid reagent that does not affeet the reaetion. An example is the removal of an aeid formed by reaetions in the gas phase using hydroxide solutions. From the reaetion stoiehiometry and measurements of the total pressure as a funetion of time, it is possible to determine the extent of the reaetion and the partial pressure or eoneentrations of the reaetant and produet speeies at the time of measurement. 

Pressure measurements can be accomplished by any one of a number of different types of manometric devices without disturbing the system being observed. Another type of reaction system that can be monitored by pressure measurements is one in which one of the products can be quantitatively removed by a solid or liquid reagent that does not otherwise affect the reaction. For example, acids formed by reactions in the gas phase can be removed by absorption in hydroxide solutions. 

In organometallic chemistry, the use of ultrasound in liquid-liquid heterogeneous systems has been limited to Hg. The emulsification of Hg with various liquids dates to the very first reports on sonochemistry (3,203,204). The use of such emulsions for chemical purposes, however, was delineated by the extensive investigations of Fry and co-workers (205-212), who have reported the sonochemical reaction of various nucleophiles with a,a -dibromoketones and mercury. The versatility of this reagent is summarized in Eqs. (30)-(36). 

The starting reagents in Gabriel amine synthesis, N-alkylphthalimides, were obtained under the action of microwave irradiation in a solid-liquid PTC system. The reactions were conducted with high yield (50-90%) simply by mixing phthalimide... 

Addition of reagents to more than four 384-well plates is greatly expedited by the use of a semi-automated liquid-dispensing system such as the MicroFill Microplate Dispenser (BioTek Winooski, VT). 

In order to overcome the difficulties associated with the covalent hydrates, anhydrous reagent systems have been investigated, including ionic liquids <2004S2809> and NBS in tetrabutylammonium bromide <200581103>. For example, the bromination of 2-aminopyrimidine 61 with the ionic liquid l-butyl-3-methylimidazolium tribromide [(bmim)Br3] gave 2-amino-5-bromopyrimidine 62 in 96% yield after 5 min at — 10°C <2004S2809>. 

I. Sodium. Probably the best known active hydrogen remover is sodium. When used outside a vacuum system, for instance as sodium wire to dry solvents, the sodium is little more than a support for a skin of sodium hydroxide. Inside a vacuum system, however, one can prepare films of sodium metal and one can prepare really clean sodium which will give a colourless solution of sodium ethoxide (see Section 5.2.1.). The method of making sodium films for the removal of acidic compounds from liquid reagents will be described and also a very much less well-known method involving sodium vapour and colloidal sodium. 

Hydride generation (HG) systems make use of a gas-liquid separator to separate the gaseous hydrides from the liquid reagents prior to introduction... 

The use of chemiluminescence reactions for the detection of metal ions by liquid chromatography was recently reported [59,60]. The detectors made use of the chemiluminescence produced in the reaction between luminol and hydrogen peroxide which is catalyzed by transition metals. The column effluent was mixed with the reagents in order to yield the chemiluminescence. The reaction was fast and was carried out at room temperature. By varying the pH of the buffer, selectivity towards certain metals was also achieved. For example, at pH 10-11 nickel could be analyzed but lead and aluminium were inactive at pH 13-14, the converse was true [59]. Aminco-Bowman has marketed a liquid chromatographic system in which amino acids and amines are analyzed by means of the fluorescence produced on reaction with the reagent fluorescamine. Fluorescamine does not fluoresce, but it does react with primary amino groups to produce fluorescent derivatives. The reaction is instantaneous and may be carried out at room temperature, usually at pH 9. This detection system promises to be far more sensitive than the ninhydrin detection system and is much more easily adapted to HPLC. 

The one-phase liquid system is more frequently encountered since many organic reactions are carried out in solution. Direct fractional distillation may separate the product, if it is a liquid, from the solvent and other liquid reagents, or concentration or cooling may lead to direct crystallisation of the product if this is a solid. However, it is often more appropriate, whether the required product is a liquid or solid, to subject the solution to the acid/base extraction procedure outlined above and considered in detail on p. 162. This acid/base extraction procedure can be done directly if the product is in solution in a water-immiscible solvent. A knowledge of the acid-base nature of the product and of its water solubility is necessary to ensure that the appropriate fraction is retained for product recovery. In those cases where the reaction solvent is water miscible (e.g. methanol, ethanol, dimethylsulphoxide, etc.) it is necessary to remove all or most of the solvent by distillation and to dissolve the residue in an excess of a water-immiscible solvent before commencing the extraction procedure. The removal of solvent from fractions obtained by these extraction procedures is these days readily effected by the use of a rotary evaporator (p. 185) and this obviates the tedium of removal of large volumes of solvent by conventional distillation. 

This review deals only with the heterogeneous oxidation of-carbon monoxide by solid materials which show some catalytic activity or a fast surface reaction. It does not include purely stoichiometric reagents used in detection and analysis, such as iodine pentoxide, mercuric oxide, palladium salts activated by molybdenum salts, or liquid-gas systems. A review of such agents has recently been presented elsewhere (11). Furthermore, no attempt has been made to provide complete coverage of the numerous patents in this field, although a number of the more important ones are mentioned. 

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