Abstract
Electrical d.c. conductances of caesium halides as ordinarily obtained are found to be anomalous compared with the halides of the other alkali metals: (i) In the conventional relationship, log
10
σ
= log
10
σ
0
–
E
/
RT
(conductance
σ
, temperature
T
° K), the values both of
σ
0
and of the activation energy
E
are abnormally low for all the caesium halides, compared with the other alkali halides. (ii) In the neighbourhood of the transition
bcc
→
fcc
in caesium chloride at 469° C, no rise of conductance is observed, contrary to what might be expected on structural grounds if the conductance is ionic and the lattice shows premonitory break-up on approaching the transition.
E
is much the same for both polymorphs, but
σ
0
for the
fcc
lattice is about one-fiftieth that for the
bcc
lattice. (iii) Transport measurements show that much of the current flows through caesium chloride without an accompanying transport of matter. The simplest interpretation of all these anomalies is that an important part of the conductance of the caesium halides as ordinarily obtained is electronic, not ionic. Possible reasons are discussed.
Reference19 articles.
1. Barrer R. M. 1951 Diffusion in and through solids. Cambridge University Press.
2. Breckenridge R. G. 1952 Imperfections in nearly perfect crystals 219 ff. New York: John W iley and Sons Inc.
3. J . A ppl;Bremiecke C. G.;Phys.,1940
4. Proc. Roy;Rogers S. E.;Soc. A,1953
5. Harpur W. W. & Ubbelohde A. R. 1952 Nature 170 975.
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