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Title: Understanding liquid–liquid equilibria in binary mixtures of hydrocarbons with a thermally robust perarylphosphonium-based ionic liquid

Journal Article · · RSC Advances
DOI:https://doi.org/10.1039/D1RA06268A· OSTI ID:1821503
 [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemical & Biomolecular Engineering, The University of South Alabama, Mobile, Alabama 36688, USA
  2. Department of Chemistry, The University of South Alabama, Mobile, Alabama 36688, USA
  3. Department of Chemical & Biological Engineering, The University Alabama, Tuscaloosa, Alabama 35487, USA
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Binary mixtures of hydrocarbons and a thermally robust ionic liquid (IL) incorporating a perarylphosphonium-based cation are investigated experimentally and computationally. Experimentally, it is seen that excess toluene added to the IL forms two distinct liquid phases, an “ion-rich” phase of fixed composition and a phase that is nearly pure toluene. Conversely, n-heptane is observed to be essentially immiscible in the neat IL. Molecular dynamics simulations capture both of these behaviours. Furthermore, the simulated composition of the toluene-rich IL phase is within 10% of the experimentally determined composition. Additional simulations are performed on the binary mixtures of the IL and ten other small hydrocarbons having mixed aromatic/aliphatic character. It is found that hydrocarbons with a predominant aliphatic character are largely immiscible with the IL, while those with a predominant aromatic character readily mix with the IL. A detailed analysis of the structure and energetic changes that occur on mixing reveals the nature of the ion-rich phase. The simulations show a bicontinuous phase with hydrocarbon uptake akin to absorption and swelling by a porous absorbent. Aromatic hydrocarbons are driven into the neat IL via dispersion forces with the IL cations and, to a lesser extent, the IL anions. The ion–ion network expands to accommodate the hydrocarbons, yet maintains a core connective structure. At a certain loading, this network becomes stretched to its limit. The energetic penalty associated with breaking the core connective network outweighs the gain from new hydrocarbon–IL interactions, leaving additional hydrocarbons in the neat phase. The spatially alternating charge of the expanded IL network is shown to interact favourably with the stacked aromatic subphase, something not possible for aliphatic hydrocarbons.

Research Organization:
Univ. of South Alabama, Mobile, AL (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
SC0020282; CHE-1464740
OSTI ID:
1821503
Alternate ID(s):
OSTI ID: 1853547
Journal Information:
RSC Advances, Journal Name: RSC Advances Vol. 11 Journal Issue: 50; ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English

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