skip to main content

SciTech ConnectSciTech Connect

Title: Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

Kirkwood-Buff or Fluctuation Solution Theory can be used to provide experimental pair fluctuations, and/or integrals over the pair distribution functions, from experimental thermodynamic data on liquid mixtures. Here, this type of approach is used to provide triplet and quadruplet fluctuations, and the corresponding integrals over the triplet and quadruplet distribution functions, in a purely thermodynamic manner that avoids the use of structure factors. The approach is then applied to binary mixtures of water + methanol and benzene + methanol over the full composition range under ambient conditions. The observed correlations between the different species vary significantly with composition. The magnitude of the fluctuations and integrals appears to increase as the number of the most polar molecule involved in the fluctuation or integral also increases. A simple physical picture of the fluctuations is provided to help rationalize some of these variations.
Authors:
;  [1]
  1. Department of Chemistry, Kansas State University, 213 CBC Building, Manhattan, Kansas 66506 (United States)
Publication Date:
OSTI Identifier:
22416226
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 9; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BENZENE; BINARY MIXTURES; CORRELATIONS; DENSITY; DISTRIBUTION FUNCTIONS; FLUCTUATIONS; INTEGRALS; LIQUIDS; METHANOL; MOLECULES; SPATIAL DISTRIBUTION; STRUCTURE FACTORS; TRIPLETS; WATER