Reaction with SO

1 REACTIONS OF O ATOMS WITH SULFUR COMPOUNDS 3.1.1 Reactions with SO 

Although workers since Gaydon had assumed that the emission was due to the reaction between SO and O atoms, the first quantitative studies were made by Harteck et al. In a preliminary communication , they reported the results of the reaction between oxygen and CS2. The pertinent reactions were assumed to be 

They estimated fcj to be approximately 1.8 x 10 l.mole . sec . Rolfes et studied the emission in a 50-1 bulb. They produced their reactants by passing molecular oxygen through an electrical discharge and adding OCS further downstream. SO was produced by the reaction 

They obtained an absolute value for 2 by comparing the emission intensity to that of the NO-0 reaction in the same apparatus 

They found 2/ 4 = 25 to within a factor of two. Using the known value of gives 2 = 4.2 X 10 I.mole sec  

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ESR experiments employing in situ photolytic decomposition of the peroxydisulfate anion (S20g ) have been carried out to study the reaction of S04 with aliphatic sulfoxides. In the case of dimethyl sulfoxide three radicals are detected ( CHj, CH3 S02, CH2 S(0)CH3), the proportion being pH-dependent. The reaction is assumed to proceed via an initially formed radical cation (not detected) which would be rapidly hydrated to give an intermediate identical with that generated by OH addition on the sulfoxide. Such a process parallels the rapid hydration of radical cations formed from thiophene in their reactions with SO/ and... 

This number is based on the observation that in the reaction with SO], k(observed) for formation of optical density at 340 nm (where the OH adduct of benzonitrile absorbs) is proportional to [benzonitrile] up to the saturation limit ( a 20 mM, k(observed) = 5 x 10 s" ), as shown by 248 nm laser experiments... 

Radioactive lateling of this cluster and neutron activation analysis of the g)ld enabled us to determine the extent of Nnding of the cluster to the particles. The results of both analytical methods show that a spacer of minimum length of about 10 A between the -SH group of a ribosomal protein and the N-atom on the cluster is n ed for significant binding. Preliminary experiments indicate that the producte of the derivatization reaction with SOS particles can be crystallized. 

Figure 8.15 shows the pH dependence of the total rate of oxidation of S(IV) as well as the individual contributions from S02 H20, HSO ", and SO3-, respectively, under conditions where [S02] = 20 ppb and [O3] = 50 ppb. The pH dependence arises from the dependence of the values of a in Eq. (R) on [H+], As discussed earlier and shown in Fig. 8.7, the fraction of total S(IV) that exists in each of the reactive forms depends on the pH since the equilibria (11)—(13) shift with pH. As a result, the three terms in Eq. (R) predominate in different pH regimes. As expected, Fig. 8.15 shows that the reaction with SO,- predominates at high pH values, whereas that with S02 H20 and HSOJ predominates at lower pH values. 

Benzene sulfinated by reaction with SO,. Benzene sulfinic acid CftH,- SOOH formed. 

Similar spectrophotometric studies were also carried out for the ligand substitution reactions with SO [54] [56] and Cl- [56] [59]. However, the reaction rates were so fast that only the spectra at the respective equilibrated states could be observed. The gradual displacement of N02 discussed above is possible only because most of the N02 exists in its protonated form in the strongly acidic solution. Hydrolysis of axial aqua ligand was also examined spectrophotometrically [56][57]. The stepwise formation constants... 

An older method of improving the wet fastness of selected direct dyeings is their diazotisation on the fibre, followed by the reaction with so-called developers... 

It is incidental to this discussion but worth mentioning that in the course of their experiments they also determined the relative rates of NO2 reaction with SO and with O... 

REACTIONS OF OZONE WITH SULFUR COMPOUNDS 3.2.1 Reaction with SO... 

Figure 7. XPS of the catalysts deteriorated by SOji (a) after reaction without SOj (b) after reaction with SO,.

The most important class of allylic substitutions are palladium-catalyzed reactions with so-called soft nucleophiles such as stabilized carbanions or amines, and with few exceptions, the enantioselective transformations discussed in this chapter belong to this category. The mechanism of these reactions has been firmly established and a detailed picture of the catalytic cycle can be drawn [1, 2,3,4,5,6,13,14,15]. The course of allylic substitutions catalyzed by metals other than palladium is less clear and information about the intermediates involved is scarce. 

Concentrated oxidizing acids (sulfuric, perchloric or nitric acid, or mixtures thereof) are also suitable to oxidize noncovered as well as prefunctionahzed diamond materials. Both hydroxylated and carboxylated surfaces can be generated this way. However, characterizing exactly the kind of carbonyl function with either XPS or IR-spectroscopy is rather complicated. An actual example is the reaction with so-called piranha water, that is, a mixture of concentrated sulfuric acid and... 

A marked improvement was effected when it was found that the displacement reaction could be operated with trialkyl alanes and ethylene or suitable 1-alkenes (propene, 1-butene, etc.) even at 300°-350°C, if the components were allowed to react for only a very short time at a moderate pressure of alkene. In spite of the high temperature, no decomposition of the trialkyl alanes to aluminum, hydrogen, and alkenes took place. Moreover, in the high temperature reaction with so short a reaction time there were practically no side reactions, i.e., a-branched alkenes and such compounds were hardly detected (314, 326). 

Direct continuous reaction of SOs with benzene, highly successful in the case of dimethyl ether as described above, is not practical because of high sulfone formation. Indirect continuous reaction with SOs by a procedure stated to yield no sulfone has, however, been achieved by the method developed by Dennis and Bull. This process is based upon an observation made by the former that, in the presence of sulfuric acid, benzene will dissolve 2-3 per cent of its own volume of benzenesulfonic acid. This process is also designed to operate in continuous countercurrent flow in a cascade system, benzene being introduced at the bottom and a benzene solution of the sulfonic acid overflowing from the top. Concentrated sulfuric acid is added continuously at the top, and spent sulfuric acid (77 per cent) is removed at the bottom of the reactor. The spent acid may be fortified to original strength with SO3 for reuse, and the benzene is recycled after the product sulfonic acid has been extracted from it with water. This procedure is, in theory, the most efficient possible, since benzenesulfonic acid is, in... 

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