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By Marita Casasola

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36/-11 ( (1) in which cK) = —r 768;r2/! I ' 1 12 tM*)*. 71) Si ' {kTJ i) +— ; 2) BB^(JL] ! «"ic»M", (3,2) . , . , (2) 3024/2 + 4728/ + 767 _ / 1 0 in which c(2) = H— + - . 491520^4/! 1 Values of Coefficients c. 645 Hence, substituting A = h/Jme and introducing the molecular units of volume and temperature 2^Vcr3/3 and ejk , the expression for B* of the corresponding-states principle can be written: D* B _( 4 y / 4 V ^ ( 4 v72 + r A W 4 v ! " 2 Vr ( 1 ) f—V' 2 4 23/i2 (2) /2 A |; c , (f)' ++ (f) 5 * is thus not only a function of the reduced temperature but depends also on the value of A/<7 and T* =T l{e I k).

Eq. 50) shows that when pairwise interactions are corrected for orientation effects, a new term involving three-body interactions is introduced. This term cannot be expressed entirely in terms of the two-body potentials. In the virial expansion, corrections to the third virial coefficient for nonpairwise additivity in nonsymmetric molecules will be greater than in those which are symmetric, because of the additional nonpairwise additive term originating from the orientation effects in two-body interactions.

The theoretical development is useful in understanding the nature of the corrections needed by the simple corresponding-states principle, and in providing a guide to empirical extensions. Although an equation such as Eq. 48) shows the variables which must be considered, its actual use is difficult because very few experimental data are available for parameters such as quadrupole moments and nonisotropic polarizabilities. Eq. 48) is useful in showing that the (e01 kT) and (N&11V) terms of the simple corresponding-states principle must be supplemented by reduced parameters which represent ratios of orientation-dependent forces to symmetrical forces.

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