Sulfonation experiments

In sulfonation experiments the extent of reaction was determined by iodine titration for total sulfite. Solutions initially containing 0.05 to 0.20 M unsaturated acid were maintained at approximate pH values by lactate, acetate, or phosphate buffers. NaCl, CaCl2, or MgCl2 were added to give changes in ionic environment. 

C with a mixture of SO3 and nitrogen containing 10 mol %S03 (typical for our experiments in cyclone and tube reactor) in a conventional bubble column. In our stirred cell sulfonation experiments, k was found to be a factor of 10 lower than the value 1.2 10 [m/s] used in calculating Table I. Therefore Ha 1 -I- Dg g /zD m(c )Q in the stirred cell. This means that the reaction is instantaneous with respect to mass transfer in that reactor. 

As in our sulfonation experiments, there is often much doubt about the exact values of the relevant parameters (c, m, p, p, D, T) at the interface, mainly because local interface conditions differ from bulk conditions. Because of this difficulty, explicit rough approximate relations for 17 are sophisticated enough to discuss experimental results and are therefore very useful. Harriott [5] derived such a simple model for the intermediate regime between fast and instantaneous reaction. Our experiments are mainly in the instantaneous regime. Based on film theory, we derived for this regime [3]... 

Table II. Estimated values for ges-liquid interface pyrosulfonic acid concentration rise (Cjj- C ),surface temperature rise (T.-T) and reaction rata constant (k2D ) in stirred cell reactor sulfonation experiments.

Table III. Scheme o1 sulfonation experiments in cvcione reactor.

Although intended for the biochemistry lab, this experiment provides analytical students with a practical characterization analysis. Of particular interest is the use of Job s method to determine the number of TNS (2-p-toludinylnaphthalene-6-sulfonate) binding sites on calmodulin, fluorescence is measured at 475 nm using an excitation wavelength of 330 nm. 

Soluble Salt Flotation. KCl separation from NaCl and media containing other soluble salts such as MgCl (eg, The Dead Sea works in Israel and Jordan) or insoluble materials such as clays is accompHshed by the flotation of crystals using amines as coUectors. The mechanism of adsorption of amines on soluble salts such as KCl has been shown to be due to the matching of coUector ion size and lattice vacancies (in KCl flotation) as well as surface charges carried by the soflds floated (22). Although cation-type coUectors (eg, amines) are commonly used, the utUity of sulfonates and carboxylates has also been demonstrated in laboratory experiments. 

The importance of the solvent, in many cases an excess of the quatemizing reagent, in the formation of heterocyclic salts was recognized early. The function of dielectric constants and other more detailed influences on quatemization are dealt with in Section VI, but a consideration of the subject from a preparative standpoint is presented here. Methanol and ethanol are used frequently as solvents, and acetone,chloroform, acetonitrile, nitrobenzene, and dimethyl-formamide have been used successfully. The last two solvents were among those considered by Coleman and Fuoss in their search for a suitable solvent for kinetic experiments both solvents gave rise to side reactions when used for the reaction of pyridine with i-butyl bromide. Their observation with nitrobenzene is unexpected, and no other workers have reported difficulties. However, tetramethylene sulfone, 2,4-dimethylsulfolane, ethylene and propylene carbonates, and salicylaldehyde were satisfactory, giving relatively rapid reactions and clean products. Ethylene dichloride, used quite frequently for Friedel-Crafts reactions, would be expected to be a useful solvent but has only recently been used for quatemization reactions. ... 

This study also demonstrated the importance of choosing an appropriate acid to effect the cyclization of 21 in the desired direction. For example, the use of neat TFA for 72 h produced mainly 22, whereas the prevailing product from the reaction induced by camphor sulfonic acid (CSA) was identified as the other possible product 25. In an equilibration experiment, 25 underwent treatment with TFA for 72 h, giving a 12 1 mixture of 22 and 25, whereas compound 22 equilibrated to... 

Tetryl. In the manufacture of Tetryl, it is usual not to nitrate dime thy laniline directly, but to dissolve it first in coned sulfuric acid and then to nitrate the dimethylaniline sulfate so obtained. Direct nitration of dimethylaniline proceeds so violently that it can be carried out only under specialized conditions. Many years experience of Tetryl manufacture has shown that the ratio of sulfuric acid to dimethylaniline should not be lower than 3 1, since a smaller amount of sulfuric acid may be detrimental to the nitration process. However, the ratio of sulfuric acid to dimethylaniline must not be too high, otherwise Tetryl yield is decreased. Temp must be maintained between 20-45° to avoid sulfonation of the benzene ring. Care must be exercised not to leave any unreacted dimethylaniline prior to introduction of nitric acid, because of the potential violence of the dimethyl-aniline-nitric acid reaction. Consequently, continuous methods of prepn are to be preferred as they inherently minimize accumulation of unreacted dimethylaniline... 

In experiments with [sulfone]o = 3.15 x 10 5 M and excess N2H4, the reaction follows pseudo-first-order kinetics. Values of k vary with [N2H4]. Formulate the rate law and evaluate the constants therein ... 

Steady-state approximation competition experiments. The solvolysis of 2-octy lmethane-sulfonate (RX) in aqueous solutions containing azide ions yields a mixture of alcohol and azide.35 Two mechanisms should be considered ... 

When performing the two-phase titration with benzethonium chloride in alkaline medium and in the presence of phenolphthalein as indicator, not only the monosulfonates but also the di- and polysulfonates are determined [19]. The content of di- and polysulfonates is the difference between two titration results giving the amounts of total sulfonates and monosulfonates. Identifying the endpoint requires some experience. 

On the basis of the available toxicological data and experience, alkane-sulfonates are to be classified and labeled as irritant in accordance with EEC Regulations on Hazardous Substances. 

There are four main sulfonation reactor configurations applied worldwide to produce all kinds of top quality anionic surfactants from sulfur-based S03/air as the sulfonating agent. All these systems have proven and documented experience ... 

The lack of any difference in the rate of isomerization between fluoro-sulfonic acid solutions of 34 which had been thoroughly degassed, and those which were saturated with oxygen, suggests that the reaction does not proceed via a triplet mechanism. In fluorosulfonic acid no unproton-ated acid is detected, ruling out the possibility of n,7r excitation. Thus, there is little doubt in this case that it is the Tr,Tr singlet state which is the reactive species. Experiments carried out with a variety of methyl-substituted protonated cydohexadienones have likewise ruled out the... 

Whole cell OPH activity was measured by following the increase in absorbancy of p-nitrophenol from the hydrolysis of substrate (0.1 mM Paraoxon) at 400 nm (sm = 17,000 M cm ). Samples of culture (1 ml) were centrifuged at 10,000 g and 4 C for 5 min. The cells were washed, resuspended with distilled water, and 100 pi was added to an assay mixture containing 400 pi 250 mM CHES [2-(N-cyclohexylamino)ethane-sulfonic acid] buffer, pH 9.0, 100 pi 1 mM Paraoxon, and 400 pi distilled water. One unit of OPH activity was defined as pmoles Paraoxon hydrolyzed per min. Each value and error bar represents the mean of two independent experiments and its standard deviation. 

XRD analysis of the solid product showed three main peaks at 28.5 , 47.4 and 56.3 , which indicated that pure crystalline CuCl was formed [3]. Several well-known dispersants polyvinyl pyrrolidone (PVP), sodium hexameta phosphate (SHP), the sodium salt of EDTA (EDTA-Na), sodium dodecyl sulfonate (SDS), and sodium dodecyl benzene sulfonate (SDBS), were introduced to obtain a highly dispersed catalyst. The X-ray patterns obtained with these were basically the same as the patterns obtained with the solids prepared in the other experiments described here. 

The transport of toluene-4-sulfonate into Comamonas testosteroni has been examined (Locher et al. 1993), and rapid uptake required growth of the cells with toluene-4-sulfonate or 4-methylbenzoate. From the results of experiments with various inhibitors, it was concluded that a toluenesulfonate anion/proton symport system operates rather than transport driven by a difference in electrical potential (A (/), and uptake could not take place under anaerobic conditions unless an electron acceptor such as nitrate was present. 

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