Argon reaction

Use of argon - reactions carried out under argon can be opened to the atmosphere briefly ( 5 s), for the addition of other chemicals, without degradation of the inert atmosphere. 

TABLE 4 Effect of preconditioning in argon reaction of 1-pentene/argon at 300°C... 

TABLE 5 Effect of preconditioning in air/argon reaction of l-butene/H2/H20 at 360°C... 

A year ago, one could say with some confidence that the excitation functions of these symmetric charge-transfer reactions were some of the most reliably established (p. 183), to the point that the argon reaction was suggested as a calibrating standard in Section 5.2.1. Today there is considerable uncertainty which hopefully will receive attention and resolution. 

THE cvcLOBUTADENE-TETRAHEDRANE SYSTEM. A related reaction is the photoisomerization of cyclobutadiene (CBD). It was found that unsubstituted CBD does not react in an argon matrix upon irradiation, while the tri-butyl substituted derivative forms the corresponding tetrahedrane [86,87]. These results may be understood on the basis of a conical intersection enclosed by the loop shown in Figure 37. The analogy with the butadiene loop (Fig. 13) is obvious. The two CBDs and the biradical shown in the figure are the three anchors in this system. With small substituents, the two lobes containing the lone electrons can be far... 

Kinetic measurements were performed employii UV-vis spectroscopy (Perkin Elmer "K2, X5 or 12 spectrophotometer) using quartz cuvettes of 1 cm pathlength at 25 0.1 C. Second-order rate constants of the reaction of methyl vinyl ketone (4.8) with cyclopentadiene (4.6) were determined from the pseudo-first-order rate constants obtained by followirg the absorption of 4.6 at 253-260 nm in the presence of an excess of 4.8. Typical concentrations were [4.8] = 18 mM and [4.6] = 0.1 mM. In order to ensure rapid dissolution of 4.6, this compound was added from a stock solution of 5.0 )j1 in 2.00 g of 1-propanol. In order to prevent evaporation of the extremely volatile 4.6, the cuvettes were filled almost completely and sealed carefully. The water used for the experiments with MeReOj was degassed by purging with argon for 0.5 hours prior to the measurements. All rate constants were reproducible to within 3%. 

Molybdenum hexafluoride can be prepared by the action of elemental fluorine on hydrogen-reduced molybdenum powder (100—300 mesh (ca 149—46 l-lm)) at 200°C. The reaction starts at 150°C. Owing to the heat of reaction, the temperature of the reactor rises quickly but it can be controlled by increasing the flow rate of the carrier gas, argon, or reducing the flow of fluorine. 

Oxygen Difluoride as a Source of the OF Radical. The existence of the OF radical [12061 -70-0] was first reported in 1934 (27). This work was later refuted (28). The OF radical was produced by photolysis of OF2 in a nitrogen or argon matrix at 4 K. The existence of the OF species was deduced from a study of the kinetics of decomposition of OF2 and the kinetics of the photochemical reaction (25,26) ... 

Metallui ical. To prevent reaction with atmospheric oxygen and nitrogen, some metals must be shielded using an inert gas when heated or melted (94). AppHcations in metals processing account for most argon consumption and an important part of helium usage (see AfETALLURGY). 

Thermal and Photochemical Reactions. Unsubstituted ethyleneimine has astonishing thermal stabihty. The reaction of ethyleneimine diluted with argon proceeds to give a mixture of unidentified compounds only at temperatures above 400°C (339). In a flow pyrolysis system under pressures of <1.33 kPa (<10 mm Hg) on quartz wool, isomerization to give /V-methylenemethylamine and ethylideneimine was observed only ia the temperature range 510—535°C. Higher temperatures result ia fragmentation (340). 

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