Equilibria in Sulphur Dioxide Solutions

Campbell, W. Boyd; Maass, O.

doi:10.1139/cjr30-006

Cited by 40 publications

(20 citation statements)

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“…As for the ionic species, the electrical conductivity data indicate that the H30+ ions are present a t a concentration of about 0.1 M in a solution 1 M in sulphur dioxide (3). The anions, HS03-, HSzOb-, plus a much smaller amount of SO3--, must be present a t the same total concentration, although the exact proportions are difficult to determine.…”

Section: Discussionmentioning

confidence: 99%

“…that all the un-ionized sulphur dioxide in solution is combined to form HzS03, the two ionization constants were calculated from electrical conductivity data to be K 1 = 0.012 to 0.017 (2,3), and Kz = lop7 to lop6 (4,5). The above assumptions, however, were sooil proved incorrect, as evidence for the existence of unchanged SO2 molecules in aqueous solution was obtained from ultraviolet absorption spectra (6,7,8,9).…”

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confidence: 99%

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On the Nature of Sulphurous Acid

Falk¹,

Giguère²

1958

Can. J. Chem.

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Repeated attempts to detect by infrared spectrometry stable H?S03 molecules in aqueous solutions of "sulphurous acid" or in frozen mixtures of SO? and Hz0 have given only negative results. Sulphur dioxide dissolved in water esists mostly in the molec~~lar state, the HS03-and HS205-ions being formed in small amounts as a result of the equilibria SO2 + 2H2O 6 HSOB-+ I-I30+ and HS03-+ SO? 6 HS?05-.There is very little interaction between SO2 and HzO molecules in condensed phases.

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

On the Nature of Sulphurous Acid

Falk¹,

Giguère²

1958

Can. J. Chem.

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“…It has been shown (32-34) that Here, AH is the enthalpy of reaction at the molality of the solution and (da/dT),,, is the shift in the degree of dissociation in the solution with temperature. Combining [8] and [9] gives Analytic expressions for calculating AH(da/dT),,, have been derived for simple ionization or association reactions (32,33). Some of the simplifying assumptions in these derivations cannot be used when the equilibrium concentrations of all the reactants and products are of the same order of magnitude.…”

Section: Aqueous Sulfur Dioxidementioning

confidence: 99%

“…[8] to [lo]), we noted that the temperature increment imposed by any specific heat calorimeter causes a shift in a and that the contribution of this "relaxation" effect is described by the expression (32)(33)(34) where AH is the enthalpy of reaction at molality m.…”

Section: Appendix Imentioning

confidence: 99%

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Thermodynamics of aqueous carbon dioxide and sulfur dioxide: heat capacities, volumes, and the temperature dependence of ionization

Barbero¹,

Hepler²,

McCurdy³

et al. 1983

Can. J. Chem.

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. Can. J. Chem. 61, 2509Chem. 61, (1983. A flow microcalorimeter and vibrating tubc densimeter were used at 25°C to obtain apparcnt molar heat capacitics and volumes of aqueous NaHCO1, KHCO,. NaHSO,, and KHSO, from 0. I to I .O mol kg-'. aqueous CO, from 0.01 to 0.10 mol kg-' and aqueous SO, from 0.045 to 2.0 mol kg-'. The contribution of "chemical relaxation" (changes in cquilibrium state and enthalpy due to change in temperature) to thc experimental heat capacitics of aqucous SO, required special attention, leading to the derivation of a new equation for calculating this cffcct. Standard statc valucs for thc heat capacities and volurnes of aqueous CO,, SOz, HCO,.., and H S O , were obtained from the apparent molar properties by extrapolation to infinite dilution. Combining these rcsults with othcr thcrmodynamic data from the literature gave estimates of log K,", the cquilibrium constant for the first neutralization of CO, and SO?, at high temperatures. The results for CO, reproducc very accuratc literature values to within 0.2 at 200°C. The expression for the reaction SO, t O H S HS0,-, log K l h = 22.771 t 2776.0/T -8.058 log T, is consistent with the sparse and limited experimental data.

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Diffusion‐controlled chemical reactions

Toor¹,

Chiang²

1959

AIChE Journal

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Transformations are obtained which reduce the system of differential equations for certain types of diffusion-controlled reactions to the equation for pure diffusion.Simple relationships between the diffusion rate with and without reactions are presented for reversible unimolecular reactions, certain types of reversible bimolecular reactions, and irreversible reactions between species with equal diffusivities. It is shown that these relationships are independent of geometry, hydrodynamics, or boundary conditions, and so the mass transfer coefficient in the presence of reactions can be obtained from the coefficient in the absence of reactions without an explicit knowledge of the mass transfer mechanism.The reaction factor for irreversible reactions with equal diffusivities, obtained by others for specific mass transfer mechanisms, is found to be quite general and essentially independent of the mechanism.Some data on the absorption of sulfur dioxide in a laminar water jet is considered.The theory of simultaneous diffusion and chemical reaction is basic to the study of mass transfer in reacting systems. Although many systems are difficult to handle analytically, even when the reactions are rapid relative to the diffusion, a number can be considerably simplified by reducing them to pure diffusion problems. It will be shown that this reduction is possible for certain classes of reactions and that in these cases the effect of the chemical reaction on the transfer rate may be obtained even though the pure diffusion problem is too complicated to handle analytically.A combination of a differential material balance with Fick's law gives the equation for pure diffusion in an isothermal system (2) :The diffusion coefficient is assumed constant, and the substantial derivative is used in this and subsequent equations to account for any bulk motion superimposed on the system. If bulk motion is present, the term difusion-controlled reactions is used in a somewhat general sense to include diffusion-convection controlled reactions as well. The system is taken to be dilute enough so that the hydrodynamic velocities are independent of the diffusion, and it is assumed that there is no convection across the boundaries. Solutions of Equation (1) with the appropriate boundary conditions give the concentration profile of the diffusing species, which, upon application of Fick's first law a t the system boundaryyields the rate of transfer across the boundary.If the flow is turbulent, the equations can be considered to apply a t every instant of time, and the solutions give the instantaneous concentration and flux. Although many of the conclusions given S. H. Chiang is with Linde Company, Tonawands. New York. below are valid for turbulent flow, this paper is concerned specifically with a stagnant fluid or laminar flow.Equations (1) and (2) with the boundary conditions fix the diffusion rate and also yield the mass transfer coefficient. The two simplest solutions, which are used as models for mass transfer in systems such as packed towers...

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Equilibria in Sulphur Dioxide Solutions

Cited by 40 publications

References 3 publications

On the Nature of Sulphurous Acid

On the Nature of Sulphurous Acid

Thermodynamics of aqueous carbon dioxide and sulfur dioxide: heat capacities, volumes, and the temperature dependence of ionization

Diffusion‐controlled chemical reactions

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