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Electrical conductivity of potassium iodide between 200 C and room temperature

University of British Columbia

The electrical conductivity of pure KI and CdI₂-doped KI has been studied in the temperature range 200 to 23°C. Two regions A and B (corresponding to different activation energy of conductivity) are identified. The region A can be given a conventional interpretation in terms of migration of cation vacancies in the bulk, their concentration being determined by impurities. U (the energy for migration of cation vacancies) amounts to 0.96 ± 0.02 eV. Observed activation energies higher than this value are accounted for by association and precipitation effects. Association energy of cation vacancies with impurities (0.48 eV. for Cd⁺₂) and heat of solution (0.25 eV. for CdI₂) obtained here are comparable with known values for other alkali halides. Region B found in this work represents unusual behaviour and has not previously been observed in any alkali halides. The activation energy of conductivity is considerably less than the energy needed for the migration of cation vacancies in the bulk. The activation energy E(formula omitted) (for region B) is about 0.57 eV. in a single crystal and 0.38 eV. in a pure KI pellet. Such low activation energies cannot be given a similar interpretation as for region A. It is suggested that the cation vacancies are in regions of unusually high mobility such as dislocations and grain boundaries. This effect may arise partly from a lower activation energy for motion of vacancies in these regions and partly from a vacancy concentration in these regions which increases with decreasing temperature, under the control of "space- charge" effects. The value 0.57 eV. appears to refer to isolated dislocations or low angle boundaries, while the value of 0.38 eV. refers to large angle intercrystalline boundaries in a pellet. A strong piece of evidence for this suggestion comes from the conductivity runs on single crystals. In an untreated single crystal, just as in pure pellets, two regions A and B are identified but region B disappears in crystals annealed overnight and reappears in a mechanically strained crystal. Moreover, region A remains almost undisturbed in each case. This means that the conduction process in region B is governed by dislocations and grain boundaries whereas region A is governed by motion of cation vacancies in the bulk.

Text

2011-06-07

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http://hdl.handle.net/2429/35159

Chemistry

University of British Columbia

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