%0 Journal Article
%A Rocha, Marisa
A.A.
%A Kerlé, Daniela
%A Kiefer, Johannes
%A Schröer, Wolffram
%A Rathke, Bernd
%D 2020
%T Liquid–Liquid Phase Behavior of Solutions of
1,3-Diethylimidazolium Bis((trifluoromethyl)sulfonyl)amide in n‑Alkyl Alcohols
%U https://acs.figshare.com/articles/journal_contribution/Liquid_Liquid_Phase_Behavior_of_Solutions_of_1_3-Diethylimidazolium_Bis_trifluoromethyl_sulfonyl_amide_in_i_n_i_Alkyl_Alcohols/11620761
%R 10.1021/acs.jced.9b00800.s001
%2 https://acs.figshare.com/ndownloader/files/21064875
%K dynamic
%K cationic side chains
%K mixture
%K phase behavior
%K solution
%K propan -1-ol butan -1-ol hexan -1-ol
%K MD
%K miscibility
%K UCST
%K cloud point method
%K C 2 C 2 imNTf 2
%K C x mimNTf 2 IL family
%K C 3 mimNTf 2
%K octan -1-ol
%K isomeric IL C 3 mimNTf 2
%K alkyl alcohols
%K phase diagrams
%K C x mimNTf 2 family
%X The
cloud point method is applied for the characterization of the
limited miscibility of ionic liquid (IL) solutions. Here, we report
the phase behavior of binary mixtures of the ionic liquid 1,3-diethylimidazolium
bis((trifluoromethyl)sulfonyl)amide (C2C2imNTf2) with n-alkyl alcohols (propan-1-ol, butan-1-ol,
hexan-1-ol, and octan-1-ol) in a temperature range (T) of 258–386 K. The two components exhibit partial miscibility
with upper critical solution temperatures (UCSTs) between 284 and
386 K. In concordance with previous studies, a detailed shape analysis
presuming Ising behavior of the phase diagrams reveals the critical
points and further properties of the phase diagrams. The results are
compared with the isomeric IL C3mimNTf2 from
the CxmimNTf2 family. Unraveling
the influence of the molecular structure of the cation on the phase
behavior is the main focus of the present investigation. The comparison
between the two isomeric ILs, C2C2imNTf2 and C3mimNTf2, shows an increase of
the UCST for the symmetric cation. A clear trend of lifting the UCST
toward higher values is observed when dealing with longer chained n-alkyl alcohols. This behavior is put into context with
a more generalized view on the phase behavior of the CxmimNTf2 IL family. An effective number
of carbon atoms of the cationic side chains is determined for the
mixtures with different alcohols. For alcohols with chains ≤6,
the effective carbon number is constant and about 3.79, while for
octan-1-ol, a slightly lower value of 3.55 was observed. That gives
evidence of a change of the molecular ordering of the system. The
experimental study is supported by molecular dynamics (MD) simulations
to attain a better understanding at the molecular level. The local
dynamics and structures are analyzed in detail and reveal the effect
of the symmetry on different physicochemical properties.
%I ACS Publications