The Chemistry of Iodine in Containment

Recent investigations of iodine behavior under radiolytic conditions have demonstrated that kinetics, not thermodynamics, will govern iodine speciation and partitioning under conditions typical of those expected in a reactor containment during an accident. In the presence of radiation, iodine volatility is orders of magnitude higher than that expected based on thermodynamic calculations. Kinetic studies have contributed extensively to the existing database of iodine chemistry and have several implications for modeling iodine behavior for safety analyses. For example, as a result of these investigations, many uncertainties in the iodine database, such as those regarding thermal oxidation of iodine, which were formerly regarded as reactor safety issues, are now considered to be relatively unimportant. In contrast, previously unconsidered factors, such as the effect on aqueous chemistry of impurities originating from surfaces, are now recognized as playing major roles in determining iodine volatility. An updated review of the existing literature regarding iodine behavior is provided, with a focus on recent developments. A critical evaluation of the data in the context of developing a model for iodine behavior under reactor accident conditions is also provided.

[1]  E. C. Beahm,et al.  Organic Iodide Formation During Severe Accidents in Light Water Nuclear Reactors , 1987 .

[2]  M. Dole 13 – Oxidation of Irradiated Polymers , 1973 .

[3]  D. Tevault,et al.  Matrix reactions of ozone and oxygen atoms with hydrogen iodide. HOI formation , 1978 .

[4]  A. K. Postma,et al.  Review of organic iodide formation under accident conditions in water- cooled reactors , 1972 .

[5]  Y. Chia CHEMISTRY OF +1 IODINE IN ALKALINE SOLUTION (thesis) , 1958 .

[6]  B. Bielski,et al.  Reactions of hydroperoxo and superoxide with iodine and bromine and the iodide (I2-) and iodine atom reduction potentials , 1986 .

[7]  J. Paquette,et al.  A Description of the Chemistry of Aqueous Solutions of Uranium and Plutonium to 200°C Using Potential-pH Diagrams , 1981 .

[8]  J. C. Wren,et al.  Corrosion of stainless steel by gaseous I2 , 1999 .

[9]  D. A. Palmer,et al.  Spectral characterization and kinetics of formation of hypoiodous acid in aqueous solution , 1986 .

[10]  H. Sims,et al.  Temperature dependence of the equilibrium constant for iodine hydrolysis at temperatures between 25 and 120 °C , 1990 .

[11]  D. Cubicciotti,et al.  Characterization of deposits on inside surfaces of lwr cladding , 1978 .

[12]  R. E. Robertson,et al.  SOLVOLYSIS IN HYDROGEN AND DEUTERIUM OXIDE: III. ALKYL HALIDES , 1959 .

[13]  R. E. Adams,et al.  REACTIONS OF IODINE VAPOR WITH ORGANIC PAINT COATINGS. , 1970 .

[14]  R. A. Hasty Partition coefficient of methyl iodide between vapor and water , 1968 .

[15]  H. A. Liebhafsky THE CATALYTIC DECOMPOSITION OF HYDROGEN PEROXIDE BY THE IODINE-IODIDE COUPLE. II AND III. THE RATE OF OXIDATION IN NEUTRAL, AND IN ACID, SOLUTION OF HYDROGEN PEROXIDE BY IODINE , 1932 .

[16]  M. Dole The radiation chemistry of macromolecules , 1972 .

[17]  M. B. Carver,et al.  Computed and experimental product concentrations in the radiolysis of water , 1980 .

[18]  H. Liebhafsky,et al.  Rate of the Dushman reaction at low iodide concentrations. Experimental method and temperature coefficient , 1972 .

[19]  J. C. Wren,et al.  The Interaction of Iodine with Organic Material in Containment , 1999 .

[20]  G. Buxton,et al.  Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O− in Aqueous Solution , 1988 .

[21]  F. Garisto Ideal gas thermodynamic properties of hypoiodous acid , 1983 .

[22]  R. Schwarzenbach,et al.  Environmental Organic Chemistry , 1993 .

[23]  C. A. Pelletier,et al.  Surface effects in the transport of airborne radioiodine at light water nuclear power plants. Final report , 1978 .

[24]  F. A. Fortunato,et al.  Spectrophotometric study of the rate of the aqueous iodate-iodide reaction , 1975 .

[25]  J. Ogilvie Intense Vibrational Absorption Spectra of Trapped Triatomic Radicals , 1973, Nature.

[26]  J. Tyler Surface analysis using X-ray photoelectron spectroscopy of iodine deposits on 17% Cr/12% Ni and mild steel surfaces oxidised in CO2CH3I gas mixtures , 1989 .

[27]  L. J. Lyons,et al.  Kinetics of iodine hydrolysis in unbuffered solutions , 1988 .

[28]  E. A. Moelwyn-Hughes The Hydrolysis of the Methyl Halides , 1938 .

[29]  Chien-chang Lin Volatility of iodine in dilute aqueous solutions , 1981 .

[30]  G. Buxton,et al.  Radiation-induced redox reactions of iodine species in aqueous solution. Formation and characterisation of III, IIV, IVI and IVIII, the stability of hypoiodous acid and the chemistry of the interconversion of iodide and iodate , 1985 .

[31]  J. C. Wren,et al.  Steady-state γ-radiolysis of aqueous methyl ethyl ketone (2-butanone) under postulated nuclear reactor accident conditions , 2000 .

[32]  D. L. Morrison,et al.  FISSION-PRODUCT DEPOSITION AND ITS ENHANCEMENT UNDER REACTOR ACCIDENT CONDITIONS: DEVELOPMENT OF REACTIVE COATINGS. One of Three Separate Final Reports on Task 3. , 1969 .

[33]  Q. G. Mulazzani,et al.  A kinetic model for radiation treatment of combustion gases , 1987 .

[34]  J. Halpern THE PRINCIPLE OF EQUIVALENCE CHANGE IN OXIDATION–REDUCTION REACTIONS , 1959 .

[35]  E. Grovenstein,et al.  KINETIC ISOTOPE EFFECT IN THE IODINATION OF 2,4,6-TRIDEUTEROPHENOL , 1957 .

[36]  J. Sigalla,et al.  Cinétique et mécanisme de l’oxydation de l’iodure par l’oxygène dissous , 1957 .

[37]  Manfred Eigen,et al.  The Kinetics of Halogen Hydrolysis , 1962 .

[38]  R. Būhler,et al.  The radical ion complex IOH−: Spectrum and reactions studied by pulse radiolysis of aqueous iodide solutions , 1976 .

[39]  R. D. Collins,et al.  AIR CLEANING FOR REACTORS WITH VENTED CONTAINMENT. , 1967 .

[40]  D. Mackay,et al.  Mass transfer coefficient correlations for volatilization of organic solutes from water. , 1983, Environmental science & technology.

[41]  I. Epstein,et al.  Kinetics of iodine hydrolysis , 1993 .

[42]  V. Salares,et al.  Photo-oxidation of Iodomethane in Solid Argon , 1975 .

[43]  E. Berliner The current state of positive halogenating agents , 1966 .

[44]  V. Salares,et al.  PHOTO‐OXIDATION OF IODOMETHANE IN SOLID ARGON , 1975 .

[45]  J. C. Wren,et al.  Iodine chemistry in the +1 oxidation state. II. A Raman and uv–visible spectroscopic study of the disproportionation of hypoiodite in basic solutions , 1986 .

[46]  S. Mezyk Rate constant and activation energy determination for reaction of e−(aq) and •OH with 2-butanone and propanal , 1994 .

[47]  J. McKelvey,et al.  Aromatic halogenation. IV. Kinetics and mechanism of iodination of phenol and 2,6-dibromophenol , 1973 .

[48]  R. W. Ramette,et al.  Triiodide ion formation equilibrium and activity coefficients in aqueous solution , 1984 .

[49]  G. Buxton,et al.  Radiation-induced redox reactions of iodine species in aqueous solution , 1985 .

[50]  Q. G. Mulazzani,et al.  Radiation treatment of combustion gases: Formulation and test of a reaction model , 1985 .

[51]  I. Barnes,et al.  FTIR spectroscopic observation of gaseous HOI , 1992 .