Bisulfite Ion Research Articles

A method for measuring the reactivity of absorbents for wet flue gas desulfurization

A sequential batch procedure for measuring the reactivity of flue gas desulfurization (FGD) limestone/lime absorbents by measuring the reaction rate with sulfuric acid is presented. It is shown that the method will predict the behavior of the absorbent in a wet FGD plant equipped with air oxidation of the bisulfite ion. With the method, sequential reactivity constants are obtained. If these constants are combined with a shrinking particle calculation, mass transfer coefficients are obtained. The reactivity constants obtained by means of the method presented can provide important information which can be used for comparing different types of absorbents with each other and for optimization of the absorbent grinding procedure.

Bisulfite ion-catalyzed transamination of cytosine residues with alpha, omega-alkanediamines: the effect of chain length on the reaction kinetics.

Pseudo-first-order rate constants for the bisulfite ion-catalyzed transamination of cytidine with 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,6-hexanediamine have been determined. Hydrolytic deamination has been shown to compete with transamination under acidic conditions, but is of minor importance at pH > 5.3 when the total concentration of diamine is greater than 0.2 mol dm-3. The dependence of the transamination rate on pH and the concentration of diamine and bisulfite ion indicates that the major reaction involves nucleophilic attack of the diamine monocation on the N3 protonated bisulfite adduct of cytidine. The effect of the chain length of the diamine on the rate of transamination is discussed, and the results are compared with those obtained by reacting single-stranded DNA with the same diamines and labeling the transaminated product with a europium chelate.

Charge reversal (CR) and neutralization reionization ( −NR +) mass spectrometry of bicarbonate and bisulfite ions

Bicarbonate (HOCO − 2) and bisulfite (HOSO − 2) ions, generated by termolecular reactions of OH − with CO 2 and SO 2, respectively, are subjected to collision experiments, in the course of which corresponding radicals HOXO . 2 (X = O on S) and cations HOXO + 2 are generated and characterized by means of tandem mass spectrometry.

Kinetics and mechanism of the oxidation of bisulfite by peroxymonosulfate

The oxidation of bisulfite ion is of importance in flue gas desulfurization processes and in the conversion of gaseous SO[sub 2] into acid rain in water droplets in the atmosphere. The oxidation of bisulfite ion by peroxymonosulfate ion, HSO[sub 5][sup [minus]], to form sulfate ion has been studied in the pH region 3.8-7.9. The reaction HSO[sub 5][sup [minus]] + HSO[sub 3][sup [minus]] [yields] 2SO[sub 4][sup 2[minus]] + 2H[sup +] was found to obey the rate law -d[HSO[sub 5][sup [minus]]]/dt = [l brace]k[sub a][alpha][sub H[sup +]] + k[sub b][alpha][sub H[sup +]][sup [minus]1] + k[sub c][r brace][l brace]HSO[sub 5][sup [minus]][HSO[sub 3][sup [minus]]], where [alpha][sub H[sup +]] is the activity of hydrogen ion. At 25[degrees]C and ionic strength 0.0050 M the rate constants k[sub a], k[sub b], and k[sub c] have the values 1.27 [times] 10[sup 7], 6.4 [times] 10[sup [minus]5], and 55 M[sup [minus]1] S[sup [minus]1], with the activity of hydrogen ion taken to be dimensionless. For the reaction path corresponding to the k[sub a] term, 90% of the reaction yields the intermediate pyrosulfate ion, S[sub 2]O[sub 7][sup 2[minus]], which then hydrolyzes with about a 1-min lifetime to sulfate and hydrogen ions. Similarly the k[sub c] path forms mostly S[sub 2]O[sub 7][supmore » 2[minus]] as an intermediate. The k[sub b] path appears to all go directly to sulfate ion. Possible mechanisms for the various reaction paths are discussed. 25 refs., 4 figs., 3 tabs.« less

Displacement Band Chromatography of Hydrogen Sulfites for Enrichment of Sulfur Isotopes

Experimental studies were conducted on the enrichment of sulfur isotopes by displacement band chromatography. In these studies, a band of hydrogen sulfite (bisulfite) ions from a sulfurous acid or bisulfite-salt solution was continuously displaced by bisulfate ions from a sulfuric acid or bisulfate-salt solution in a column packed with aminated polystyrene-divinyl benzene resin under varied process conditions. The sulfur isotopes were enriched through isotopic exchange between the bisulfite ions on the resin and the sulfurous acid and/or bisulfite-salt solution in contact with the resin within the moving band. During the isotopic exchange, S-34 isotope was favored in the resin phase and S-32 isotope in the liquid phase. As a result, the S-34 isotope was gradually enriched at the rear of the band, and S-32 isotope at the front. The effects of the various process conditions were evaluated on separative power, height equivalent to a theoretical plate, and operational simplicity. The highest separative power, 3.05 g S-34/cm{sup 3}/yr, was achieved with an ammonium bisulfite feed displaced by a sulfuric acid displacer at 65{degrees}C operating temperature.

Amino acid end‐group in commercial heparin. III. Determination of the number of amino groups of amino acid and hexosamine residues per heparin molecule

AbstractThe reactions of heparin with 2,4,6‐trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP‐amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP‐amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α‐amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α‐amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc.

Gas-phase thermochemical properties of the bicarbonate and bisulfite ions

A combined experimental and theoretical study of the gas-phase thermochemical properties of bicarbonate ion HOCO − 2, bisulfite ion HOSO − 2, and their conjugate acids is presented. The formation and qualitative identification of the sulfonate ion HSO − 3 is also reported. Threshold energies for collision- induced dissociation of OH − ion from HOCO − 2 and HOSO − 2 have been determined to be 50.3 ± 2.5 and 61.3 ± 2.5 kcal mol −1 respectively, from which the standard heats of formation Δ H° f,298 [HOCO − 2, g] = −177.8 ± 2.5 kcal mol −1 and δH° f,298 [HOSO − 2] = −165.6 ± 2.5 kcal mol −1 are derived by means of simple thermochemical cycles. The measured HO − binding energies of CO 2 and SO 2 are in good agreement with ab initio calculations and with the expected values based on empirical correlations between Brönsted and Lewis basicities of negative ions. Reactions between bicarbonate ion and a series of neutral acids in the flowing afterglow indicate an apparent proton affinity of 356 ± 2 kcal mol −1. Bicarbonate ion reacts with H 2S to produce both HS − and HS −(H 2O), and the deuterium-labelled ion, DOCO − 2, reacts also by H/D exchange. Bisulfite ion is found to have an apparent proton affinity of 337 ± 3 kcal mol −1 from its behavior in proton transfer reactions with a series of reference acids. The reaction between HOSO − 2 and HCl yields Cl −(SO 2) as the major ionic product, along with a small amount of Cl −. DOSO − 2 does not exhibit any H/D exchange with HCl or carboxylic acids. Sulfonate ion can be formed at room temperature in the flowing afterglow either by oxygen atom transfer from NO 2 to HSO − 2, or by hydride transfer from CH 3O − to SO 3. High level ab initio calculations predict gas-phase acidities (Δ H acid) for carbonic acid (HO) 2CO and sulfurous acid (HO) 2SO of 339 and 330 kcal mol −1 respectively, and enthalpy changes for their dehydration of −5 and −2kcal mol −1 respectively. The origin of the large differences between the calculated and apparent basicities of HOCO − 2 and HOSO − 2 is proposed to be due, in part, to a dissociative neutralization mechanism wherein dehydration of the nascent carbonic acid and sulfurous acid molecules accompanies proton transfer.

Modeling of the chemistry of wet limestone flue gas desulfurization systems

The chemistry of wet limestone flue gas desulfurization (FGD) systems is complicated by the interaction of dissolved SO 2 and dissolved nitrogen ocides. A substantial number of nitrogen-sulfur compounds can be formed from the reactions of sulfite and bisulfite ions with nitrogen oxyanions. A computer model is used to simulate the kinetics and to determine the effect of scrubber operating conditions on the production of nitrogen-sulfur compounds. With increasingly stringent regulations covering solid and liquid waste disposal, it is important to minimize undesirable byproducts in FGD systems. The modeling is also used to study the effect of scrubber conditions on the production of N 2 O (nitrous oxide). Emission of N 2 O into the atmosphere is undesirable because it has both significant ozone depletion potential and global warming potential

Electrochemistry of the oxidation of sulfite and bisulfite ions at a graphite surface: an overall approach

An investigation of the electrochemical oxidation of sulfite and bisulfite ions dissolved in a sodium electrolyte solutions at a graphite surface was undertaken. The study relies upon linear voltammetry and the importance of the various oxidative processes occuring at the graphite surface, namely electrochemical of residual organic groups, carbon oxides and oxygen evolution, as well as the oxidation of tetravalent sulfur oxidation. The i—E curves relevant to bisulfite and the sulfite oxidation are modeled by the simple Butler—Volmer law for irreversible direct proceses even though the oxidation scheme has not yet been elucidated. Confidence intervals of the determined parameters, diffusion coefficient, exchange current density, and charge-transfer coefficient are estimated.

The interaction of bisulfite with milk xanthine oxidase.

Bisulfite ion competitively inhibits xanthine oxidase activity. The ability of HSO3- to bind at the molybdenum center is controlled by pH due to a pKa of 6.91 for SO3(2-)/HSO3-. The Kd for the enzyme-bisulfite complex is 4.5 x 10(-5) M at pH 7.0 and 25 degrees C. The relative magnitude of extinction changes in the optical absorption spectra, the number of inhibitor ions reversibly bound, and the number of electrons required for complete bleaching of the visible spectrum of the milk xanthine oxidase-HSO3- complex were all dependent on the percentage of fully functional xanthine oxidase. Binding of HSO3- causes perturbations of the visible spectrum: the maximum extinction changes at 320 and 422 nm were calculated to be -4300 and -2150 M-1 cm-1, respectively. The stoichiometry of reversible binding was determined to be one molecule of HSO3-/active molybdenum center. Combined optical and EPR analyses of anaerobic dithionite titrations revealed that the relative redox potentials of the Mo6+/5+ and Mo5+/4+ couples decreased by approximately 35 and 45 mV on binding bisulfite, respectively. The finding that bisulfite has a profound effect on the redox properties of xanthine oxidase necessitates a re-evaluation of dithionite titrations previously carried out with this enzyme at neutral and low pH values since bisulfite produced as an oxidation product of dithionite binds to the enzyme during the course of titration.

Selective transport of aldehydes across an anion-exchange membrane via the formation of bisulfite adducts

Organic nonelectrolytes can be selectively transported through an ion-exchange membrane if they are specifically converted to electrolytes in the membrane. Aldehydes react with bisulfite to form hydroxyalkanesulfonates (HASA), which are the conjugate bases of strong acids. Aldehydes are shown to be transported efficiently across an anion-exchange membrane via the coupled counter-transport of HMSA ion with hydroxide ion and the relay of an aldehyde from one membrane-bound bisulfite ion to another. Permeation rates are in the order of formaldehyde > acetaldehyde > acetone; this relationship parallels the relative order of the stability constants for formation of the respective adducts with bisulfite ion. Aldehydes can be separated readily from other organic solutes by this method.

Mechanism of thyroid peroxidase inhibition by ethylenethiourea

Ethylenethiourea (ETU) is a thyroid carcinogen present in foods formed by degradation and metabolism of ethylenebis[dithiocarbamate] fungicides. ETU inhibits thyroid peroxidase (TPX), the enzyme that catalyzes synthesis of thyroid hormones. Inhibition of TPX-catalyzed reactions by ETU occurs only in the presence of iodide ion with concomitant oxidative metabolism to imidazoline and bisulfite ion. Inhibition ceases upon consumption of ETU with no loss of enzymatic activity and negligible covalent binding of ETU to TPX. TPX inhibition by ETU is unlike that for derivatives of imidazoline-2-thione, which cause suicide inactivation via covalent binding to the prosthetic heme group. These results demonstrate a metabolic route for detoxication of ETU in the thyroid and suggest that low-level or intermittent exposure to ETU would have minimal effects on thyroid hormone production.

Studies on the stability of Kathon® CG/ICP Microbicide in alpha olefin sulfonate Based systems

AbstractKathon® CG/ICP Microbicide (Rohm & Haas Co.) which contains 1.5% 5‐chloro‐2‐methyl‐4‐isothiazolin‐3‐one and 0.35% 2‐methyl‐4‐isothiazolin‐3‐one as active ingredients has been found to be a highly efficient antimicrobial preservative for formulated products. However, its use has been contra‐indicated for formulations containing certain anionic surfactants, especially AOS, because of the suspected presence of residual bisulfite ion added to remove residual hypochlorite remaining at the end of the bleaching process.It has been found that sulfite ion is not stable in the complex mixture of components in commercially produced AOS. AOS samples tested, whether bleached or not, contained residual reducing capacity, but of a sufficiently low redox potential as to not affect Kathon® CG/ICP Microbicide stability.Alternative analytical methods for analysis for bisulfite in AOS and other surfactant systems are discussed.A new HPLC method for determination of Kathon® CG/ICP Microbicide level in formulated products was developed.

Reaction of ferrous chelate nitrosyl complexes with sulfite and bisulfite ions

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReaction of ferrous chelate nitrosyl complexes with sulfite and bisulfite ionsDavid Littlejohn and Shih Ger ChangCite this: Ind. Eng. Chem. Res. 1990, 29, 1, 10–14Publication Date (Print):January 1, 1990Publication History Published online1 May 2002Published inissue 1 January 1990https://doi.org/10.1021/ie00097a002RIGHTS & PERMISSIONSArticle Views289Altmetric-Citations24LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (639 KB) Get e-Alerts Get e-Alerts

Oxidation of bisulfite ion by oxygen

Etude de l'oxydation de l'ion bisulfite, avec formation d'un intermediaire S 2 O 7 2− qui s'hydrolyse en SO 4 2− , H + et/ou HSO 4 2−

Evaluation of the mechanism of dilauryl thiodipropionate antioxidant activity

AbstractDilauryl thiodipropionate (DLTDP) was ineffective as an antioxidant for decomposing lipid hydroperoxides when incorporated into fish oil at concentrations less than 50,000 ppm (0.1 M) at 50 C. However, some general antioxidant properties for DLTDP were observed in fish oil containing 200 ppm DLTDP at 50 C under oxygen for 72 hr. An anomolous prooxidant behavior for DLTDP in fish oil was observed under some conditions of accelerated oxidation which was attributed to the formation of the bisulfite ion free radicals derived from DLTDP degradations. DLTDP was effective for inactivating peracids in model systems containing performic acid and nonanal, ethyl oleate or cholesterol. In these systems DLTDP (2:1 DLTDP:performic acid mole ratio) was preferentially oxidized to the sulfoxide, and prevented the formation of nonanoic acid, 9‐epoxy ethyl oleate and 5,6‐epoxy cholesterol, respectively.

Mechanism-based inhibition of lactoperoxidase by thiocarbamide goitrogens. Identification of turnover and inactivation pathways

Direct evidence is presented in support of mechanism-based (suicide) inactivation of lactoperoxidase by thiocarbamide thyroid inhibitors. The turnover of 1-methylbenzimidazolidine-2-thione was demonstrated by identifying the inhibitor-derived products 1-methylbenzimidazole and bisulfite ion that are formed concurrent to enzyme inactivation. The turnover of a hydroperoxide cosubstrate, 5-phenyl-4-pentenyl hydroperoxide, was quantitated from formation of the corresponding alcohol during enzyme inactivation. A specific inactivation pathway is suggested by the covalent binding of 1 mol of 14C- and 35S-labeled benzimidazolidine-2-thione and 1-methylbenzimidazolidine-2-thione per mole of inactivated lactoperoxidase. These results are explained by partitioning of inhibitor-derived S-oxygenated intermediates between turnover and inactivation pathways. The properties of the inactivation process are unique among thiono-sulfur compounds and suggest that benzimidazolinesulfenic acids are the reactive intermediates.

The roles of pH and ionic species in sulfur dioxide- and sulfite-induced bronchoconstriction.

Sulfur dioxide (SO2) and sulfites are well-described causes of bronchoconstriction in persons with asthma that are chemically related and, therefore, may share a common mechanism of action. When either sulfur species dissolves in aqueous solutions, a pH-dependent equilibrium is established predominantly among bisulfite ion (HSO3-), sulfite ion (SO3=), and SO2. In addition, hydrogen ions may be released. To assess the relative bronchoconstricting potencies of these chemical forms and the role of acidity caused by the release of hydrogen ions in SO2- and sulfite-induced bronchoconstriction, we administered to 10 asthmatic subjects nebulized sodium sulfite (Na2SO3) solutions at pH 9 containing 95% sulfite, at pH 6.6 containing 80% bisulfite, and at pH 4 containing 99% bisulfite but greater than an order of magnitude more SO2 than the pH 6.6 solutions. Subjects inhaled increasing concentrations of aerosolized Na2SO3 at each pH during 1 min of tidal breathing. Subjects also breathed buffered acetic acid aerosols with the same acidity of the pH 4 Na2SO3 solutions to control for the airway effects of acid aerosols. To assess sensitivity to SO2 gas, subjects inhaled increasing concentrations of SO2 during eucapneic hyperpnea. Bronchoconstrictor response was assessed by measuring specific airway resistance (SRaw) before and after each challenge. Nine of the 10 subjects developed bronchoconstriction after inhaling the Na2SO3 aerosols at all 3 levels of pH and the SO2 gas. The mean concentration of Na2SO3 solution calculated to increase SRaw by 100% above baseline was significantly different (p less than 0.01) at the various levels of pH: pH 4 (0.17 mg/ml) less than pH 6.6 (0.49 mg/ml) less than pH 9 (2.10 mg/ml).(ABSTRACT TRUNCATED AT 250 WORDS)

Disulfate Ion as an Intermediate to Sulfuric Acid in Acid Rain Formation

The oxidation of the bisulfite ion by dissolved oxygen to produce sulfate ion involves the formation of a previously undetected intermediate. This intermediate has a fairly strong Raman band at 1090 wave numbers and a weak Raman band at 740 wave numbers, both of which are probably due to sulfur-oxygen stretches. The intermediate is proposed to be the disulfate ion S(2)O(7)(2-), which hydrolyzes into H(+) and either SO(4)(2-) or HSO(4)(2-) with a half-life of about 52 seconds at 25 degrees C.

Effect of water on the formation of bisulfite ions upon sulfur dioxide adsorption onto faujasite-type zeolites

SO/sub 2/ adsorption onto faujasite-type zeolites (Na-X, Na-Y) was investigated by combined UV and IR spectroscopy. Formation of chemisorbed HSO/sub 3//sup -/ species, indicated by a UV band around 215 nm and a low-frequency IR band at 1240 cm/sup -1/, was shown to depend significantly upon the presence of water. Differences in the behavior of Na-X and Na-Y were discussed in terms of different site populations.