Entropy and Fluid-Fluid Separation in Nonadditive Hard-Sphere Mixtures: The Asymmetric Case
Entropy and Fluid-Fluid Separation in Nonadditive Hard-Sphere Mixtures: The Asymmetric Case
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非加性硬球混合物中的熵和液-液分离：不对称情况
DOI：
10.1021/jp013150k
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发表时间：
2002
影响因子：
3.3
通讯作者：
P. Giaquinta
中科院分区：
文献类型：
--
作者：
F. Saija;P. Giaquinta
我们报告的Monte Carlo模拟结果的热力学和结构性质的二元非加性混合物的硬球的尺寸没有太大的不同。在已知流体-流体分离与冷冻竞争的参数范围内进行模拟。我们研究了发病的结构有序的一个阶段的计划所提供的剩余多粒子熵，一个综合措施的权重的空间相关性，涉及两个以上的粒子在系统的构型熵。这种方法已经在对称情况下进行了测试[Saija，F.; Pastore，G.; Giaquinta，P.V.J. Phys. Chem. B 1998，102，10368]。本研究证实了一个相当少量的非加和性可能会显着影响的相行为的混合物也在热力学制度中，渗透耗竭效应不起主导作用的指示。
We report Monte Carlo simulation results for the thermodynamic and structural properties of binary nonadditive mixtures of hard spheres with not too dissimilar sizes. The simulations were carried out over a range of parameters where fluid-fluid separation is known to compete with freezing. We investigated the onset of structural ordering in a one-phase scheme as that provided by the residual multiparticle entropy, an integrated measure of the weight of spatial correlations involving more than two particles in the configurational entropy of the system. This approach has been already tested in the symmetric case [Saija, F.; Pastore, G.; Giaquinta, P. V. J. Phys. Chem. B 1998, 102, 10368]. The present study confirms the indication that a rather small amount of nonadditivity may significantly influence the phase behavior of the mixture also in a thermodynamic regime where osmotic depletion effects do not play a leading role.