Kinetics of Recombination of Iodine Atoms (Englisch)

in The Journal of Chemical Physics ; 4 , 8 ; 497-504
The Journal of Chemical Physics

(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.

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