Sulfur ratio effects

Figure 13. Impact energy at 100% ductile fracture temperature, which is shelf energy, as a function of REM-to-sulfur ratio retained in the 80,000 psi steel. Note the progressive effect of increasing REM additions on the transverse impacts while the longitudinal values remain virtually unchanged. The X points represent untreated steel.

The effect of the accelerator to sulfur ratio on the vulcanisation chemistry was also investigated by comparing the vulcanisation products from conventional, SEV and EV formulation systems. With increase in accelerator to sulfur ratio (from conventional to EV) there is a lowering in the sulfur rank. Also, the cis-to-trans isomerisation increases with the amount of accelerator. 

For 1,3-butadiene hydrogenation, the toxicity of sulfur is 3 (Fig. 13). which is lower than the toxicity for olefin hydrogenation. The hydrogenation of 1-butyne has also been studied for various ratios of sulfur over palladium. As was already published (86), the 1-butyne hydrogenation rate increases with time. The same effect has been observed on sulfided palladium. The turnover number is consequently presented for 1-butyne hydrogenation versus the sulfur content for various 1-butyne conversions (see Fig. 14). During the first minutes of reaction (0-25% conversion), the toxicity of sulfur appears close to 1 the rates are proportional to the free surface. However, at higher conversion, the rate becomes independent from the sulfur ratio. The toxicity is zero. 

Petsch and Berner (1998) expanded the model of Van Cappellen and Ingall (1996) to include the sulfur system, as well as carbon and sulfur isotope effects. This study examined the response of the C-S-O-Fe-P system, and in particular carbon and sulfur isotope ratios, to perturbation in global ocean overturn rates, changes in continental... 

The effect of added hydrochloric acid concentration was studied in order to determine whether or not the acid had any effect on pyrite and ash removal, sulfate-to-sulfur ratio, final heat content, and possible chlorination of the coal. Coal has many basic ash constituents, so increased ash removal was expected, as well as some suppression of the sulfate-to-sulfur ratio because the reaction that results in sulfate formation also yields eight moles of hydrogen ion per mole of sulfate (common ion effect). Added acid was studied in the range of 0.0 to 1.2M (0.0, 0.1, 0.3, and 1.2M) hydrochloric acid in 0.9M ferric chloride. Duplicate runs were made at each concentration with all four coals for a total of 32 runs. The results showed no definite trends (except one-uide infra) even when the data were smoothed via computer regression analysis. Apparently the concentration range was not broad enough to have any substantial effect on the production of sulfate or to cause the removal of additional ash over that which is removed at the pH of IM ferric chloride ( pH 2). 

Radiotracer analysis is particularly effective for tracking the fate of additives, because molecular fragmentation can typically be expected to result in an impurity element distribution different from that of the original molecules. For example, in nickel plating in the presence of thiourea, complete incorporation of the molecule should give a carbon/sulfur ratio of 1.0, while experiments indicate a ratio ranging from 0.01 to 0.7 depending on the deposition conditions [130,131,141,142], As with additive incorporation, the decomposition process can be a sensitive function of the co-adsorbates [145, 149, 150]. 

SiMe3)2, should be a triply charged cation. However, there is no evidence of any counterions, and it is assumed therefore that there is a nonstoichiometric silver-to-sulfur ratio. This situation is not surprising, because such an effect is also observed in binary Ag2S. 

Aluminum to sulfiir ratios in residues point to iron co-precipitation, such that an alunite-jarosite compound is formed, typically about two-thirds alunite and one-third jarosite. The sodium plus potassium to sulfur ratios indicate that 10 to 20% of the alunite-jarosite is in the hydronium form. Kyle [27] gives a useful summary of these phenomena while Johnson and co-workers [15, 16] have carried out detailed studies into the effects of alkali addition and leach liquor salinity on PAL. Some typical assays are shown in Table 2 and Table 3. 

X-ray photoelectron spectroscopy (XPS) has been used to measure the nitrogen-sulfur ratio of the PAH/PSS multilayers, as a function of the number of deposited layers [88,92,93]. This ratio shows a pronounced odd-even trend with the number of deposited layers, being higher when PAH is the outermost layer, and lower when PSS is the outermost layer. This trend is maintained even for high numbers of layers, and reveals an effective stratification of the multilayers. Contact angle measurements [88,92,93] also show a pronounced odd-even trend in the measured angles. 

Hgure 9-46. Effect of wash-water/sulfur ratio on iron content of SuiFerox suifur fiitercake. (l an/C/eec/rarH/AftV7S3e-4/no/i/, 1990 ... 

The fusion of Adamsite with sulfur is effected in hermetic vessels [7]. The weight ratio, Adamsite to sulfur, is from 1 4 to 1 5. In the early phase of the fusion process, the temperature is maintained at 160 C for 2 hours it is then raised to 200 C for one hour. The Adamsite/sulfur fusion process, which furnishes a solid reaction product, probably occurs according to the scheme ... 

Coal Hquefaction iavolves raising the atomic hydrogen-to-carbon ratio from approximately 0.8/1.0 for a typical bituminous coal, to 2/1 for Hquid transportation fuels or 4/1 for methane (4). In this process, molecular weight reduction and removal of mineral matter and heteroatoms such as sulfur, oxygen, and nitrogen may need to be effected. 

Scheme 6 depicts a typical penicillin sulfoxide rearrangement (69JA1401). The mechanism probably involves an initial thermal formation of a sulfenic acid which is trapped by the acetic anhydride as the mixed sulfenic-acetic anhydride. Nucleophilic attack by the double bond on the sulfur leads to an episulfonium ion which, depending on the site of acetate attack, can afford either the penam (19) or the cepham (20). Product ratios are dependent on reaction conditions. For example, in another related study acetic anhydride gave predominantly the penam product, while chloroacetic anhydride gave the cepham product (7lJCS(O3540). The rearrangement can also be effected by acid in this case the principal products are the cepham (21) and the cephem (22 Scheme 7). Since these early studies a wide variety of reagents have been found to catalyze the conversion of a penicillin sulfoxide to the cepham/cephem ring system (e.g. 77JOC2887).

Products of Combustion For lean mixtures, the products of combustion (POC) of a sulfur-free fuel consist of carbon dioxide, water vapor, nitrogen, oxygen, and possible small amounts of carbon monoxide and unburned hydrocarbon species. Figure 27-12 shows the effect of fuel-air ratio on the flue gas composition resulting from the combustion of natural gas. In the case of solid and liquid fuels, the... 

Only within the past few years have serious attempts been made to estimate quantitatively the differences in reactivity between thiophene and benzene and between the 2- and 3-position of thiophene. Careful investigation on the acid-induced exchange of deuterium and tritium have shown that the ratios of the exchange rates in the 2- and 3-positions are 1045 61 for deuterium and 911 60 for tritium in 57% by weight aqueous sulfuric acid at 24.6°C. A kinetic isotope effect in the isotopic exchange has been found to be k-r/kr, = 0.51 0.03 in the 2-position and kr/kjy — 0.59 0.04 in the... 

The acid cleavage of the aryl— silicon bond (desilylation), which provides a measure of the reactivity of the aromatic carbon of the bond, has been applied to 2- and 3-thienyl trimethylsilane, It was found that the 2-isomer reacted only 43.5 times faster than the 3-isomer and 5000 times faster than the phenyl compound at 50,2°C in acetic acid containing aqueous sulfuric acid. The results so far are consistent with the relative reactivities of thiophene upon detritia-tion if a linear free-energy relationship between the substituent effect in detritiation and desilylation is assumed, as the p-methyl group activates about 240 (200-300) times in detritiation with aqueous sulfuric acid and about 18 times in desilylation. A direct experimental comparison of the difference between benzene and thiophene in detritiation has not been carried out, but it may be mentioned that even in 80.7% sulfuric acid, benzene is detritiated about 600 times slower than 2-tritiothiophene. The aforementioned consideration makes it probable that under similar conditions the ratio of the rates of detritiation of thiophene and benzene is larger than in the desilylation. A still larger difference in reactivity between the 2-position of thiophene and benzene has been found for acetoxymercuration which... 

Figure 8 Effect of acid concentration on the grafting of cotton linters. [KMn04] = 0.06 N [monomer] = 1 mol/g cell liquor ratio 1 50 T = 50°C t = 1 h. (—) Oxalic acid (----) sulfuric acid.

From the results of other authors should be mentioned the observation of a similar effect, e.g. in the oxidation of olefins on nickel oxide (118), where the retardation of the reaction of 1-butene by cis-2-butene was greater than the effect of 1-butene on the reaction of m-2-butene the ratio of the adsorption coefficients Kcia h/Kwas 1.45. In a study on hydrogenation over C03O4 it was reported (109) that the reactivities of ethylene and propylene were nearly the same (1.17 in favor of propylene), when measured separately, whereas the ratio of adsorption coefficients was 8.4 in favor of ethylene. This led in the competitive arrangement to preferential hydrogenation of ethylene. A similar phenomenon occurs in the catalytic reduction of nitric oxide and sulfur dioxide by carbon monoxide (120a). 

Sources of thermochemical data for such calculations are Vol 7, H38 Lff Heat Effects — Data for Common Explosives NBS Circular 500 (Ref 39a) Cox Pilcher (Ref 89) and the studies of Rhodes Nelson (Ref 24b) and McKinley Brown (Ref 28a) on mixed acids As an example of such a calculation we will compute the heat evolution and temp rise occurring during the mixed acid nitration of glycerol to NG. We will assume that a typical 50/50 nitric acid/sulfuric acid MA is used and that the MA/glycerol ratio is 5/1. Further assumptions are that all the glycerol is converted to NG, and that the heats of soln of NG in die. spent acid, and of spent acid in the NG, are negligibly small (cf discussion of these effects by the writer in Ref 51). The net reaction is then ... 

The other fragmentation pathways are typical for diaryl sulfoxides1-4-6,1. A corresponding ortho effect was found in chlorodiphenyl ethers and sulfides but not in sulfones12 (12) were the sulfinate ester rearrangements1-4,6,11 and the consequent formation of the m/z 125 and m/z 159 ions suppress the other possible fragmentations of the molecular ions (equation 4). It is also noteworthy that the ratio [m/z 125] [m/z 159] increases with increasing distance between the chlorine and the sulfur (equation 4). 

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