Sulfite oxidation

A number of chemical reactions occur in the absorber beginning with the reaction of limestone (CaCO,) with the SO, to form calcium sulfite (CaSO,). The calcium sulfite oxidizes to calcium sul-... 

In spite of its wide application, the mechanisms of this reaction remain obscure. Many diverse arguments have been published since the reaction was first investigated in 1897 (Bl, C5, C9, F7, J6, M5, P9, R2, S5, W2, W4, Yl, Y4). Cooper et al. (C9) introduced this method as a yardstick for the measurement of volumetric mass-transfer coefficients in gas-liquid contacting. Karow et al. (Kl) later concluded that the sulfite oxidation is suitable for fermentation process scale-up studies. Cooper et al. established that the reaction proceeds at a rate independent of sulfite ion concentration over wide concentration ranges. In their work they considered the sulfite oxidation to be of zero order with respect to both sulfite and sulfate concentration. 

Measurement of the absorption rate of carbon dioxide in aqueous solutions of sodium hydroxide has been used in some of the more recent work on mass-transfer rate in gas-liquid dispersions (D6, N3, R4, R5, V5, W2, W4, Y3). Although this absorption has a disadvantage because of the high solubility of C02 as compared to 02, it has several advantages over the sulfite-oxidation method. For example, it is relatively insensitive to impurities, and the physical properties of the liquid can be altered by the addition of other liquids without appreciably affecting the chemical kinetics. Yoshida and... 

In 1960, Yoshida et al. (Y4), working with a geometrically similar system and with the sulfite-oxidation method, confirmed the results reported by Cooper et al. They also showed that the gas film does not offer any resistance to the mass transfer of oxygen from air to the sodium sulfite solution. In addition, they found that the mass-transfer coefficient per unit area was equal for water and for aqueous sodium sulfite. 

Stirred-slurry operation, 120-123 holdup, axial dispersion, 122-123 mass transfer, 120-122 reactors, 80 Subcooling, 236-238 inlet, 261 Subreactors, 363 Sulfite-oxidation, 300-301 Summerfield, combustion equation, 44-43 Surface-active agents, 327-333 experiment, 327-329 theory, 329-333... 

Nowadays economy and ecology render the reuse of the sulfite solution increasingly important. Normally the scrubber liquor is recovered as dilution water directly in the neutralization of sulfonation plant or in the slurry preparation unit of synthetic detergent plants. In some special cases, when the presence of sulfites is incompatible with the slurry composition, it is possible to install as optional a sulfite oxidation unit. This oxidation takes place with atmospheric air. 

Drivers for Performing Sulfite Oxidation in Micro Reactors... 

The sulfite oxidation is a recommended test reaction for determining the size of the specific interfacial area in gas/liquid systems, in particular as expressed by the a value [9, 10]. 

Beneficial Micro Reactor Properties for Sulfite Oxidation... 

The sulfite reaction is used for the above-mentioned purpose and hence is an analytical tool for judging micro-reactor performance [5,9,10]. The sulfite oxidation as a chemical method provides complementary information to optical analysis of the specific interfacial area. 

Sulfite Oxidation Investigated in Micro Reactors Cas/liquid reaction 27 [CL 27] Oxidation of sulfite to sulfate... 

GL 27] [R 3] ]P 29] By means of sulfite oxidation, the specific interfacial area of the fluid system nitrogen/water was determined at Weber numbers ranging from lO " to 10 [10]. In this range, the interface increases from 4000 m m to 10 000 m m . The data are - with exceptions - in accordance with optically derived analysis of the interface and predictions from calculations. At stiU larger Weber number up to 10, the specific interfacial area increases up to 17 000 m m, which was determined optically. 

Sulfite-bisulfite-metabisulfite-sulfurous acid system, 23 672 Sulfite ester, 23 651 Sulfite lignins, 75 15-18 Sulfite oxidation kLaL measurement method, 75 679... 

Biochemically, Mo draws attention because it is an essential enzyme cofactor in nearly all organisms, with particular importance for nitrogen fixation, nitrate reduction and sulfite oxidation. Such biochemical ubiquity is surprising in view of the general scarcity of Mo at the Earth s surface. 

The scheme (Fig. 15.1) thus explained the production of both sulfate and sulfur in equimolar amounts from thiosulfate oxidation. In showing adenylylsulfate as an intermediate, it also provided a feasible route for the conservation of energy from sulfite oxidation by a substrate-level phosphorylation mechanism, in which ADP sulfurylase and adenylate kinase give rise to ATP ... 

Figure. 15.2. Mechanism for the introduction of into sulfate formed during sulfite oxidation by the activities of APS reductase and ADP sulfurylase. Modified from Peck and Stulberg (1962).

Kappler U, Dahl C. 2001. Enzymology and molecular biology of prokaryotic sulfite oxidation. FEMS Microbiol Lett 203 1-9. 

Martin, L. R., Kinetic Studies of Sulfite Oxidation in Aqueous Solutions, in S02, NO, and N02 Oxidation Mechanisms Atmospheric Consideration, Acid Precipitation Series, pp. 63-100 and references therein (J. I. Teasley, Series Ed.), Butterworth, Stone-ham, MA, 1984. 

Sulfite Oxidation Method The sulfite oxidation method is a classical, but still useful, technique for measuring /cgfl (or [4]. The method is based on the air oxidation of an aqueous solution of sodium sulfite (Na SOg) to sodium sulfate (Na.,SO ) with a cupric ion (Cu " ") or cobaltous ion (Co ) catalyst. With appropriate concentrations of sodium sulfite (about 1 N) or cupric ions (>10 inolH ), the value of k for the rate of oxygen absorption into sulfite solution, which can be determined by chemical analysis, is practically equal to Zr, for the physical oxygen absorption into sulfate solution in other words, the enhancement factor E, as defined by Equation 6.20, is essentially equal to unity. 

It is a well-known fact that bubbles produced by mechanical force in electrolyte solutions are much smaller than those in pure water. This can be explained by reduction of the rate of bubble coalescence due to an electrostatic potential at the surface of aqueous electrolyte solutions. Thus, k a values in aerated stirred tanks obtained by the sulfite oxidation method are larger than those obtained by physical absorption into pure water, in the same apparatus, and at the same gas rate and stirrer speed [3]. Quantitative relationships between k a values and the ionic strength are available [4]. Recently published data on were obtained mostly by physical absorption or desorption with pure water. 

Culture media usually contain some electrolytes, and in this respect the values of A in these media might be closer to those obtained by the sulfite oxidation method than to those obtained by experiments with pure water. 

The sodium sulfite oxidation method (Cooper et al., 1944) is based on the oxidation of sodium sulfite to sodium sulfate in the presence of catalyst (Cu++ or Co++) as... 

The sodium sulfite oxidation technique has its limitation in the fact that the solution cannot approximate the physical and chemical properties of a fermentation broth. An additional problem is that this technique requires high ionic concentrations (1 to 2 mol/L), the presence of which can affect the interfacial area and, in a lesser degree, the mass-transfer coefficient (Van t Riet, 1979). However, this technique is helpful in comparing the performance of fermenters and studying the effect of scale-up and operating conditions. 

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