Kinetics of Recombination of Iodine Atoms (English)

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In: The Journal of Chemical Physics   ;  4 ,  8  ;  497-504  ;  1936

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(1) The equilibrium I2+hv→I+I; I+I→I2 was studied in presence of different foreign gases by means of a sensitive optical arrangement. (2) The equilibrium is a ``heterogeneous'' one at low pressure, the atoms recombining mainly by diffusing to the walls. In this region, the dissociation increases with rising pressure. (3) At higher pressure (about 250 mm in He, 40 mm in CO2, etc.), the recombination becomes homogeneous. The transition is a sharp one, and practically no influence of the walls is observed at pressures above the transition point. (4) In the region of homogeneous recombination, the dissociation is exactly proportional to the square root of light intensity and to the inverse square root of pressure, in accordance with the theoretical formulae for the ``recombination by three‐body collisions,'' I+I+X→I2+X. (5) The velocity constants of these reactions are calculated for different gases X. The values are given in Table IV. The order of increasing efficiency in promoting recombination is He, A, H2, N2, O2, CH4, CO2, C6H6. One double collision I+I in 530 is a recombining one in helium, and one in 50 in carbon dioxide at atmospheric pressure. (6) The efficiency as third body is higher for the di‐ and polyatomic molecules than for the monoatomic ones, and increases with growing molecular size and the intensity of the molecular fields of the colliding particles.

Table of contents – Volume 4, Issue 8

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The Reactions of Deuterium Atoms with Methane and Ethane
Steacie, E. W. R. / Phillips, N. W. F. | 1936
The Absorption Spectrum of Methyl Alcohol Vapor in the Photographic Infrared
Badger, Richard M. / Bauer, Simon H. | 1936
The Continuous Absorption Spectrum of Bromine: A New Interpretation
Acton, A. P. / Aickin, R. G. / Bayliss, N. S. | 1936
The Theoretical Treatment of Chemical Reactions Produced by Ionization Processes Part I. The Ortho‐Para Hydrogen Conversion by Alpha‐Particles
Eyring, Henry / Hirschfelder, J. O. / Taylor, Hugh S. | 1936
The Electron Affinity of Bromine Atoms from Space‐Charge Effects
Glockler, Geo. / Calvin, Melvin | 1936
The Limiting High Temperature Rotational Partition Function of Nonrigid Molecules VI. The Methanol Equilibrium
Kassel, Louis S. | 1936
Kinetics of Recombination of Iodine Atoms
Rabinowitch, E. / Wood, W. C. | 1936
The Homogeneous Unimolecular Decomposition of Gaseous Alkyl Nitrites VI. The Decomposition of n‐Butyl Nitrite
Steacie, E. W. R. / Smith, W. McF. | 1936
The Normal Vibrations and the Isotope Effect of Molecules of the Type X2YN with an N‐Fold Axis of Symmetry
Schimmel, Herbert | 1936
Transfer of Rotational Energy in Molecular Collisions I. Elementary Processes Which Lead to Abnormal Rotation of the HgH Molecule
Rieke, F. F. | 1936
The Effect of Rotational Distortion on the Thermodynamic Properties of Water and Other Polyatomic Molecules
Wilson, E. Bright | 1936
Thermodynamic Properties of Phosphorus Compounds
Anderson, Thomas F. / Yost, Don M. | 1936
Atomic Dimensions from the Coefficients of Compressibility and Thermal Expansion
Djang, G. F. | 1936
The Structure of Rubrene and Some Remarks on the ``Ortho‐Effect''
Bergmann, E. / Herlinger, E. | 1936
The Raman Spectra of Deutero‐acetones and Methyl Alcohol‐d
Bates, J. R. / Anderson, Leigh C. / Halford, J. O. | 1936
Raman Spectrum of Deutero‐Acetaldehyde
Wood, R. W. | 1936
Preliminary Note on the Phase Relationships in the Nickel‐Tin System
Fetz, Erich / Jette, Eric R. | 1936