Chemical reactions, data base

Chemical Kinetic Data Base for Propellant Combustion I. Reactions Involving NO, N02, HNO, HN02, HCN, and N20, Tsang, W and Herron,... 

W. Tsang. Chemical Kinetic Data Base for Propellant Combustion II. Reactions Involving CN, NCO and HNCO. J. Phys. Chem. Ref. Data, 21 753-791,1991. 

Thomas JK (1967) Pulse radiolysis of aqueous solutions of methyl iodide and methyl bromide. The reactions of iodine atoms and methyl radicals in water. J Phys Chem 71 1919-1925 Tsang W, Hampson RF (1986) Chemical kinetic data base for combustion chemistry, part I. Methane and related compounds. J Phys Chem Ref Data 15 1086-1279 UlanskiP, von Sonntag C (1999) The OFI-radical-induced chain reactions of methanol with hydrogen peroxide and with peroxodisulfate. J Chem Soc Perkin Trans 2 165-168 Ulanski P, Bothe E, Hildenbrand K, von Sonntag C, Rosiak JM (1997) The influence of repulsive electrostatic forces on the lifetimes of polyfacrylic acid) radicals in aqueous solution. Nukleonika 42 425-436... 

FIGURE 6 Effect of chemical reaction on liquid-phase mass transfer coefficient (assumes bimolecular irreversible reaction). [Data based on Van Krevelen, D. W., and Hoftijzer, P. J. (1948). Rec. Trav. Chim. 67, 563.]... 

In considering the limitions of disk storage we must further consider the data base of chemical reactions which must be available to the program We have mentioned the number 25,000 as the number of synthetic reactions now existing. This is the present size of the file of Derwent.(2) Naturally, of these 25,000 the most popular 2000 are used more than all of the rest put together. Nonetheless, many molecules of interest have something special about them so that their synthesis may require an unusual reaction. Finally we observe that there is an enormous store of literature observations about reactions which show us that such and such a reaction is inappropriate when such and such a substructure is present because the desired reaction proceeds at a slower rate than that of a side reaction. These must in principle and sooner or later in fact be incorporated into any useful reaction data base. 

The literature search for this review turned out to be complicated. Reaction data bases such as REACCS or ChemInformRX worked well but, as expected, could not give a complete survey of the relevant literature. Chemical Abstracts key words such as sulfur extrusion or desulfurization revealed numerous references dealing with industrial desulfurization of stock chemicals in addition to the citations of interest nevertheless, these turned out to be incomplete (for similar problems in searching for sulfur extrusion reactions, see 90MI2). 

CA Selects is a series of current awareness publications derived from the Chemical Abstracts data base. For each topic in the series, a special profile assures the retrieval of pertinent abstracts. The CA Selects series topic that is most relevant to chemical labeling needs is Chemical Hazards, Health eind Safety. This current-awareness service covers documents dealing with safety in the chemical industry, as well as the health and safety of personnel working with hazardous substances. Coverage includes effects of human exposure to hazardous substances and hazardous properties of chemical substances and reactions. The annual cost for this service is 75.00. 

Laser-induced fluorescence data provide a wide variety of detailed information about physical and chemical reactions. Laser-based time-resolved (picosecond) fluorescence spectroscopic techniques have been used to investigate the mechanism of photo-stabilisation by UVAs such as benzophenones, ben-zotriazoles and polymer-bound UV stabilisers [117]. Such ultrafast spectroscopic measurements can provide insight into the dynamics of the primary energy dissipation processes in polymers and polymer additives following light absorption. Excimer LIF spectra of plasticised PVC showed two distinct regions... 

Helman, W.P. and Ross, A.B. (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH/0 ) in aqueous solution. Chemical kinetic data base for combustion chemistry. Part 3 Propane. Journal of Physical Chemistry Reference Data, 17, 513-882. 

Company Chemical Structure and Reaction Data Bases... 

Many additional refinements have been made, primarily to take into account more aspects of the microscopic solvent structure, within the framework of diffiision models of bimolecular chemical reactions that encompass also many-body and dynamic effects, such as, for example, treatments based on kinetic theory [35]. One should keep in mind, however, that in many cases die practical value of these advanced theoretical models for a quantitative analysis or prediction of reaction rate data in solution may be limited. 

The different internal and external file formats make it necessary to have programs which convert one format into another. One of the first conversion programs for chemical structure information was Babel (around 1992). It supports almost 50 data formats for input and output of chemical structure information [61]. CLIFF is another file format converter based on the CACTVS technology and which supports nearly the same number of file formats [29]. In contrast to Babel, the program is more comprehensive it is able to convert chemical reaction information, and can calculate missing atom coordinates [29]. 

Over 25 years ago the coking factor of the radiant coil was empirically correlated to operating conditions (48). It has been assumed that the mass transfer of coke precursors from the bulk of the gas to the walls was controlling the rate of deposition (39). Kinetic models (24,49,50) were developed based on the chemical reaction at the wall as a controlling step. Bench-scale data (51—53) appear to indicate that a chemical reaction controls. However, flow regimes of bench-scale reactors are so different from the commercial furnaces that scale-up of bench-scale results caimot be confidently appHed to commercial furnaces. For example. Figure 3 shows the coke deposited on a controlled cylindrical specimen in a continuous stirred tank reactor (CSTR) and the rate of coke deposition. The deposition rate decreases with time and attains a pseudo steady value. Though this is achieved in a matter of rninutes in bench-scale reactors, it takes a few days in a commercial furnace. 

Those based on strictly empirical descriptions Mathematical models based on physical and chemical laws (e.g., mass and energy balances, thermodynamics, chemical reaction kinefics) are frequently employed in optimization apphcations. These models are conceptually attractive because a gener model for any system size can be developed before the system is constructed. On the other hand, an empirical model can be devised that simply correlates input-output data without any physiochemical analysis of the process. For... 

When the kinetics are unknown, still-useful information can be obtained by finding equilibrium compositions at fixed temperature or adiabatically, or at some specified approach to the adiabatic temperature, say within 25°C (45°F) of it. Such calculations require only an input of the components of the feed and produc ts and their thermodynamic properties, not their stoichiometric relations, and are based on Gibbs energy minimization. Computer programs appear, for instance, in Smith and Missen Chemical Reaction Equilibrium Analysis Theory and Algorithms, Wiley, 1982), but the problem often is laborious enough to warrant use of one of the several available commercial services and their data banks. Several simpler cases with specified stoichiometries are solved by Walas Phase Equilibiia in Chemical Engineering, Butterworths, 1985). 

The second group of chemical methods is based on a comparison of the structure (s) of the reaction product(s) with that of the starting material. These methods can be illustrated by the observation that l-methylpyrid-2-onimine (38) is formed when 2-aminopyridine (37) is allowed to react with methyl iodide followed by treatment with alkali. From these data it was incorrectly concluded that 2-aminopyridine reacted, or existed, in the imino form. Actually, the... 

The effective interfacial area is used in mass transfer studies as an undivided part of individual and overall coefficients when it is difficult to separate and determine the effective area. The work of Shulman et.al.,65 presents a well organized evaluation of other work in addition to their own. One of the difficulties in correlating tower packing performance lies in obtaining the correct values for the effective interfacial areas of the packing on which the actual absorption, desorption, chemical reaction, etc. are completed. Figures 9-47 A, B, C, D, E, F, G present a correlation for Avater flow based on the ammonia-water data of Fellinger [27] and are valid for absorption work. 

The acidity of a solution has pronounced effects on many chemical reactions. It is therefore important to be able to learn and control the hydrogen ion concentration. This control is obtained through application of the Equilibrium Law. Common types of calculation, based on this law, are those needed to determine KA from experimental data and those using KA to find [H+], We will illustrate both of these types, using benzoic acid, QH6COOH, as an example. 

While there is a vast range of different drug structures, there are only a relatively small number of chemical reactions, some of which are shown below in Table 5.13 (p. 199), involved in the production of metabolites. Based on the structure of the drug, it is therefore possible to predict the most likely metabolites. Use may then be made of reconstructed ion chromatograms (RlCs) of mlz values corresponding to the predicted molecular weights of these metabolites to locate them within the LC-MS data obtained. 

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