The Five Alkali Metals under High Pressure

Effect of high pressure on the melting constants, electrical resistance and volume of the alkali metals.---(1) New data for Rb and Cs, presented in detail elsewhere, are given in three tables. Then, since similar data have previously been obtained for Li, Na and K, the results of a comparative study of all five alkali metals under pressure are given and discussed. (2) Melting constants. The general character of the melting phenomena is the same for the alkali metals as for other substances; the melting curve continues to rise indefinitely with increasing pressure, with neither maximum nor critical point. Above 10000 kg/${\mathrm{cm}}^{2}$ there is a reversal of the normal melting points of Na and K, and a moderate graphical extrapolation indicates other reversals also, so that at high pressures we may expect a complete reversal of the order of normal melting temperatures, Cs being the highest and Li the lowest. The fractional change of volume on melting is the same within 25 percent for Na, K, Rb, and Cs, as is also the latent heat of melting per gm atom; for Li the values are only about one-fourth as large. (3) Electric resistance. K shows the greatest relative decrease of resistance with pressure above 1400 kg/${\mathrm{cm}}^{2}$; Rb occupies electrically an intermediate position between K and Cs. The effect of pressure on the resistance of Cs is unique in that there is a minimum (at 4000 kg/${\mathrm{cm}}^{2}$). This minimum seems to have no connection with the crystal structure of the solid, but will probably be shown by the liquid also at higher pressures. At low pressures Cs has the maximum negative pressure coefficient of resistance and at high pressures the maximum positive coefficient of all pure metals measured. At high pressures the curve of pressure coefficient of resistance of Cs against pressure has a point of inflection which could not be predicted from the behavior at lower pressures; if other metals behave similarly above the present experimental range, it is possible that the resistance of all metals will eventually pass through a minimum. Such a change for Rb may be expected below 20000 kg/${\mathrm{cm}}^{2}$. This reversal of resistance may be an indication of the first beginning of a quantum break-down, suggested more strongly by the volume relations. The discontinuity of resistance at melting is approximately constant for all the alkalies. (4) Volume. Cs is the most compressible solid element yet measured directly. Instead of the atom the electron seems to be the significant unit of structure for volume since the volume per electron and the compressibility per electron do not vary greatly throughout the alkali series, whereas atomic volume and atomic compressibility vary greatly. At atmospheric pressure the electronic volume of K is abnormal, standing between that of Li and Na, but at high pressures there is a reversal. At high pressures the electronic compressibilities of all the alkalies are roughly equal (2.2. to 3.5\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}29}$ at 12000 kg/${\mathrm{cm}}^{2}$), except for K, which is twice as compressible per electron (5.9\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}29}$). The initial high relative compressibilities of Cs and Rb decrease rapidly with pressure, crossing that for K below 8000 kg/${\mathrm{cm}}^{2}$, while the high compressibility of K persists over a wide pressure range with comparatively small drop. All the evidence indicates an abnormally open electronic structure for K. (5) Comparison with compressibility of electron gas. Numerically the compressibility of all the alkalies is of the order of magnitude of that of a perfect gas under a high internal pressure, taking the electron as the gas unit. For K, the compressibility has passed a turning point within the experimental range, and appears to be ultimately headed for the perfect gas value. This may be the beginning of the quantum break-down, which is complete only at remotely high pressures. On the theoretical side, Schottky's theorem, in conjunction with the extrapolated behavior of compressibility, indicates the same break-down at high pressures.