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408 C.M. COLINA et al. FIGURE 2 Density vs. pressure diagram for carbon dioxide. Continuous lines predicted by the Span–Wagner EOS [6], dashed lines predicted by the 2CLJQ EOS [3 – 5], and symbols this work: (B) 288.37 K, (A) 330.39 K, (V) 374.31 K, (S) 478.71 K, (O) 546.83 K, (K) 692.60 K, (X) 855.57 K and (W) 952.33 K. change assuming an homogeneous density for r . rc : Acceptance probabilities of displacement and volume changes were adjusted to be about 30%. Averages were taken over 5 £ 105 cycles, after a stabilization period of at least 3 £ 105 cycles. RESULTS Results for Volumetric Properties Figure 2 shows the simulated densities as a function of pressure in comparison with the values predicted from the Span–Wagner EOS and the 2CLJQ EOS for eight isotherms, one of them ðT 1⁄4 288:37 KÞ corresponding to the sub-critical region. This figure shows an excellent agreement between the 2CLJQ EOS and our simulations results, except at the highest densities. Stoll et al. [23] carried out an extensive comparison of molecular simulation results of 30 individual 2CLJQ fluids, with different values of L and Q*2, against the 2CLJQ EOS. It should be mentioned that the quadrupolar contribution of the 2CLJQ EOS is assumed to be L independent and was obtained for L 1⁄4 0:505: They observed increas- ing deviations in the VLE predictions for fluids as L departs from 0.505; in particular, they found that the EOS systematically under-predicts the saturated liquid densities and the critical flatness of the phase envelope. Figure 2 shows that the 2CLJQ EOS for FIGURE 3 Volume expansivity (bP) vs. pressure. Legend as in Fig. 2.PDF Image | Thermal Properties of Supercritical Carbon Dioxide
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