On Molecular Sound Velocity of Liquids. III : Consideration on the Rao's Relation on the Dependence of Molecular Sound Velocity on Critical Constants
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概要
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(a) Theoretical derivation of the Rao's relation Rv=a(T_c/M)^<1/6>v_c has been performed on the basis of the Lennard-Jones and Devonshire's liquid model and using Wentorf. Buehler, Hirschfelder and Curtiss' equation of state. Here Br means the molecular sound velocity defined by Rv=(M/ρ)V^<1/3>, with M the molecular weight, ρthe density and V the sound velocity; T_c and v_c mean the critical temperature and the critical volume respectively, and a is an empirical constant with average value 2.68, according to Rao. The theoretical value of a obtained in this paper is 4.64. (b) Re-examination of Rao's relation has been performed on organic liquids and on some liquified gases employing existing ultrasonic velocity data and the following average values have been obtained: a_<exp>=2.86 (on five liquified gases), a_<exp>=2.69 (on 21 organic liquids except alcohols, acids and acetonitrile). The a_<exp> for alcohols and acids are somewhat lower, the lowest example being a_<exp>=1.825 for acetic acid. These substances are known to be associated liquids and show extremely low values of R_v, deviating from the additivity rule of Br for atomie increments or bond increments. This is also the cause for the low values of a_<exp> in alcohols and acids. The average value for 27 organic liquids including alcohols, acids and acetonitrile are a<exp>= 2.60. (c) A modification of Rao's relation has been proposed in the form Rv=b(γTc/M)^<1/0>v_c, where T means the ratio of the specific heats. The constant b is theoretically 4.44 and the average experimental value for 3 liquified gases proved to be 2.53, and for 13 organic liquids 2.53. The average value for 11 organic liquids excluding alcohols and acids proved to be 2.56.
- 社団法人日本物理学会の論文
- 1954-02-25
著者
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NOMOTO Otohiko
Kobayasi Institute of Physical Research
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Kishimoto Tadashi
Kobayashi Institute Of Physical Research
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Nomoto Otohiko
Kobayashi Institute Of Physical Research
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