The kinetics of oxygen exchange between the sulfite ion and water

Betts, R. H.; Voss, R. H.

doi:10.1139/v70-339

Cited by 80 publications

(71 citation statements)

References 3 publications

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“…H+ + SO~-, J (Sillen, 1964), where g 1 and K2 are the equilibrium constants for reactions (A3) and (15), respectively. The dissociation of (SO2 "H20)t and HSO~ are very rapid, and equilibrium is for all intents and purposes instantaneously established (Beilke and Lamb (1975); see also Betts and Voss (1970), whose values update those of Eigen et al (1961).…”

Section: Discussionmentioning

confidence: 99%

On the scavenging of SO2 by cloud and raindrops: I. A theoretical study of SO2 absorption and desorption for water drops in air

Walcek

Pruppacher

1983

J Atmos Chem

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An extention of our previous theory for trace gas absorption into freely-falling cloud and raindrops is presented. This theory describes the convective diffusion of a trace gas through air and into a water drop with internal circulation, the drop falling at its terminal velocity. Using flow fields for the circulating water inside and for the moving air outside the drop, obtained by numerical solutions to the Navier-Stokes equation of motion, we numerically solved the convective diffusion equation to determine the uptake of SO 2 by water drops of various sizes, time exposure to the gas phase, and concentration of SO~ in the gas phase. It was found that for drops of radius larger than 1 mm and relatively low gas concentrations (< 10 ppb (v)), resistance to gas diffusion lies mainly in the gas phase; while for drops of radius less than 500 ~tm and gas concentrations larger than those found in the atmosphere (> 1% (v)), the resistance to diffusion lies primarily in the liquid phase. With drop sizes and gas concentrations between these limits, the rate of SO 2 uptake is controlled by a coupled resistance to diffusion inside and outside the drop. In addition to our general model, a simplified version was formulated which allows considerable savings in computer time for evaluation and improved ease of handling without significant loss of accuracy. A comparison between our simplified model and that of Barrie (1978) shows that the boundary-layer approach of Barrie may be a useful alternate approach to estimating trace gase absorption by water drops, provided appropriate values are chosen for the thickness of the boundary layers involved.

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Section: Discussionmentioning

confidence: 99%

On the scavenging of SO2 by cloud and raindrops: I. A theoretical study of SO2 absorption and desorption for water drops in air

Walcek

Pruppacher

1983

J Atmos Chem

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“…Kinetic [4,7] and spectroscopic [8,9] measurements have been performed to study the speciation of the dissolved SO 2 . It has been revealed that the stabilities of the two forms of 3 …”

Section: Introductionmentioning

confidence: 99%

SO2 Hydrolysis: Ab initio MD Study of the Formation of Bisulfite Ion

Stirling¹

2013

J. Comput. Chem. Jpn.

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Ab initio molecular dynamics simulations have been performed to study the dissolution of SO 2 in water. It has been obtained that the hydrated SO 2 is surrounded by the water molecules without any S-H hydrogen bond, restraining the sulfonate anion formation but allowing the bisulfite isomer formation. The metadynamics method has been employed to explore the free energy surface of the SO 2 + H 2 O reaction. The simulations revealed that the hydrated SO 2 forms bisulfite anion and hydronium cation after overcoming a ca. 17 kcal/mol free energy barrier. Direct, one-step H 2 SO 3 formation could not been observed, in sharp contrast with earlier cluster calculations. These findings indicate a step-wise H 2 SO 3 formation in water. The presence of the sulfur lone pair represents an important constraint on the mechanism: the nucleophilic H 2 O attack can occur only from certain angles as shown by the reactive trajectories.

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“…Fast dimerisation of HSO 3 ) to disulfite with a small value for the dimerisation constant (Q D = 0.088 mold m )3 ) [24,25] has been reported. Also a similar observation was made by us in Fe III (salen) (OH 2 ) 2 + -S IV redox reaction [26].…”

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confidence: 99%

Kinetics and Mechanism of the Formation of (1,5)bis(2-hydroxybenzamido)3- azapentaneiron(III) and its Reactions with Thiocyanate, Azide, Acetate, Sulfur(IV) and Ascorbic Acid in Solution, and the Synthesis and Characterization of (nitrato)bis- (2-hydroxybenzamido)3-azapentaneiron(III). The Role of Phenol–amide–amine Coordination

Nayak

Dash

Nayak

et al. 2005

Transition Met Chem

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The complexation of iron(III) with (1,5)bis(2-hydroxybenzamido)3-azapentane (H 2 L) under varying [H + ] T (0.01-0.1 mol dm )3 ) and [Fe III ] T (3.0 · 10 )4 -1.7 · 10 )2 , ½L T ¼ ð0:5 À 1:0Þ Â 10 À4 mol dm )3 ) (I=0.3 mol dm )3 , 10% v/v, MeOH + H 2 O, 25.0°C) was reversible and displayed monophasic kinetics; the dominant path involved FeOH 2+ and H 3 L + . The mechanism is essentially a dissociative interchange (I d ) and dissociation of the aqua ligand from the encounter complex, [Fe(OH 2 ) 5 OH 2+ , H 3 L + ] is rate-limiting. Equilibrium measurements indicated that the ligand binds iron(III) in a bidentate, tetradentate and pentadentate fashion under varying pH conditions. Iron(III) promoted deprotonation of the phenol moieties, and sec-NH þ 2 of the dien unit are in tune with this proposition. The octahedral coordination of ½FeðHL=LÞðOH 2 Þ 2þ=þ is further supported by the aqua ligand substitution by AcO ) , NCS ) , N À 3 =N 3 H; SO 2À 3 =HSO À 3 . However, marked pK perturbation of the bound ascorbate in [Fe(L)(HAsc/Asc)] 0/) (DpK {[Fe(L)(HAsc)] ) HAsc)} =6) is compelling evidence for chelation of HAsc ) / Asc 2) leading to unusual hepta coordination of iron(III) in the ascorbate complexes. Despite the multidentate nature of the ligand, its iron(III) complexes remain sensitive to reduction by S IV and ascorbic acid.The complex (nitrato){(1,5)bis(2-hydroxybenzamido)3-azapentane}iron(III) has been synthesised and characterised by elemental analysis, i.r. and u.v.-vis spectral measurements. The room temperature magnetic moment (l eff =4.2 BM) conforms to the intermediate spin state of iron(III) (S=3/2) which is further supported by e.s.r. measurements (77 K, g=4.2, 8.1) and the 57 Fe Mo¨ssbauer spectrum (d=0.41 mm s )1 ; D E Q ¼ 0:78 mm/s). The cyclic voltametry (MeOH, TEAP as background electrolyte) display only one quasi-reversible peak in the )0.254 to )0.4 V range (vs. SCE), the irreversibility being due to the formation of an iron(II) complex which dissociates under the experimental conditions.

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The kinetics of oxygen exchange between the sulfite ion and water

Cited by 80 publications

References 3 publications

On the scavenging of SO2 by cloud and raindrops: I. A theoretical study of SO2 absorption and desorption for water drops in air

On the scavenging of SO2 by cloud and raindrops: I. A theoretical study of SO2 absorption and desorption for water drops in air

SO2 Hydrolysis: Ab initio MD Study of the Formation of Bisulfite Ion

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