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SCIENCE CHINA Chemistry, Volume 60, Issue 9: 1243-1249(2017) https://doi.org/10.1007/s11426-017-9022-0

Stability, acidity and interaction properties of [Bmim][SbF6] coupled with concentrated sulfuric acid

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  • ReceivedJan 11, 2017
  • AcceptedFeb 15, 2017
  • PublishedMay 23, 2017

Abstract

Ionic liquid coupled with strong acid systems presents considerable promise in some catalytic fields. In the present work, the multiple complex systems composed by 98 wt% concentrated sulfuric acid and [Bmim][SbF6] were investigated in the terms of stability, acidity and interaction properties. It was found that acidolysis of [Bmim][SbF6] occurred in the 98 wt% concentrated sulfuric acid accompanied by HF releasing and SbF6 degrading to [SbF6y(HSO4)y]. The species after acidolysis in the multiple complex systems were checked and confirmed by electrospray ionization mass spectrometry (ESI-MS), Fourier transform infrared spectroscopy (FT-IR), 1H NMR and 19F NMR. Acidity increased slightly with less than 1 wt% [Bmim][SbF6] addition, while decreased with more proportion, which was determined based on the Hammett acidity functions H0, using 13C NMR. The strong hydrogen bond S–O–H···F of interaction among the multiple complex systems was confirmed by molecular dynamic simulation.


Funded by

the One Hundred Talent Program of CAS

National Natural Science Foundation of China Petroleum & Chemical Corporation Joint Fund(U1662129)

Key Program of National Natural Science Foundation of China(91434203)

Key Research Program of Frontier Sciences

CAS(QYZDY-SSW-JSC011)

and Fund of State Key Laboratory of Multiphase Complex Systems

IPE

CAS(MPCS-2015-A-05)


Acknowledgment

This work was supported by the One Hundred Talent Program of CAS, National Natural Science Foundation of China Petroleum & Chemical Corporation Joint Fund (U1662129), Key Program of National Natural Science Foundation of China (91434203), Key Research Program of Frontier Sciences, CAS (QYZDY-SSW-JSC011), and State Key Laboratory of Multiphase Complex Systems, IPE, CAS (MPCS-2015-A-05).


Interest statement

The authors declare that they have no conflict of interest.


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  • Figure 1

    Schematic of hydrogen fluoride collecting unit (color online).

  • Figure 2

    (a) ESI-MS mass spectra of [Bmim][SbF6]-H2O binary system; (b) the enlargement of 229–246 region of the spectra shown in (a); (c) the enlargement of 229–239 region of the spectra shown in (b).

  • Figure 3

    (A) FT-IR spectra of binary system in which the ratio between [Bmim][SbF6] and water is the same from (B); (B) FT-IR spectra of ternary system with different mass ratios of [Bmim][SbF6] in 98 wt% concentrated sulfuric acid. (a) X[ Bmim] [ SbF6 ] =0.5 wt%; (b) X[ Bmim] [ SbF6 ] =2.9 wt%; (c) X[ Bmim] [ SbF6 ] =4.8 wt%; (d) X[ Bmim] [ SbF6 ] =29.7 wt%; (e) [Bmim][SbF6]; (f) H2O (color online).

  • Figure 4

    Time variation of the forming of fluorine ion during the acidolysis of [Bmim][SbF6] in 98 wt% concentrated sulfuric acid.

  • Figure 5

    19F NMR spectra of the anion with different mass ratios of [Bmim][SbF6] in the multiple complex systems of [Bmim][SbF6] and 98 wt% concentrated sulfuric acid. (A) after 12 h: (a-1) X[Bmim][ SbF 6] =0.1 wt%; (b-1) X [Bmim][ SbF 6]=0.5 wt%; (c-1) X [Bmim][ SbF 6]=33 wt%; (d-1) [Bmim][SbF6]. (B) after 360 h: (a-2) X[Bmim][ SbF 6] =0.1 wt%; (b-2) X [Bmim][ SbF 6]=0.5 wt%; (c-2) X [Bmim][ SbF 6]=33 wt%; (d-2) [Bmim][SbF6] (color online).

  • Figure 6

    1H NMR spectra of the cation with different mass ratios of [Bmim][SbF6] in the multiple complex systems of [Bmim][SbF6] and 98 wt% concentrated sulfuric acid. (A) after 12 h: (a-1) 98 wt% H2SO4; (b-1) X[ Bmim] [ SbF6 ] =0.1 wt%; (c-1) X[ Bmim] [ SbF6 ] =0.5 wt%; (d-1) X[ Bmim] [ SbF6 ] =33 wt%; (e-1) [Bmim][SbF6]. (B) after 360 h: ((a-2) 98 wt% H2SO4; (b-2) X[Bmim][ SbF 6] =0.1 wt%; (c-2) X [Bmim][ SbF 6]=0.5 wt%; (d-2) X [Bmim][ SbF 6]=33 wt%; (e-2) [Bmim][SbF6] (color online).

  • Figure 7

    1H NMR spectra of S–O–H of different proportions of H2SO4 in the multiple complex systems of [Bmim][SbF6] in 98 wt% concentrated sulfuric acid. (A) after 12 h: (a-1) 98 wt% H2SO4; (b-1) X[Bmim][ SbF 6] =0.1 wt%; (c-1) X [Bmim][ SbF 6]=0.5 wt%; (d-1) X [Bmim][ SbF 6]=33 wt%; (e-1) [Bmim][SbF6]. (B) after 360 h: (a-2) 98 wt% H2SO4; (b-2) X[ Bmim] [ SbF6 ] =0.1 wt%; (c-2) X[ Bmim] [ SbF6 ] =0.5 wt%; (d-2) X[ Bmim] [ SbF6 ] =33 wt%; (e-2) [Bmim][SbF6] (color online).

  • Figure 8

    FT-IR spectra of different proportions of the multiple complex systems of [Bmim][SbF6] in the 98 wt% concentrated sulfuric acid. (a) [Bmim][SbF6]; (b) X[ Bmim] [ SbF6 ] =33 wt%; (c) X[ Bmim] [ SbF6 ] =25 wt%; (d) X[ Bmim] [ SbF6 ] =0.5 wt%; (e) X[ Bmim] [ SbF6 ] =0.1 wt%; (f) 98 wt% H2SO4 (color online).

  • Figure 9

    Calculated RDF and CNF line for cation-anion of [Bmim][SbF6] in the multiple complex systems of [Bmim][SbF6] in 98 wt% concentrated sulfuric acid. (a, b) RDF and CNF of X[Bmim][ SbF 6] =0.5 wt%; (c, d) RDF and CNF of X [Bmim][ SbF 6]=33 wt% (color online).

  • Figure 10

    Calculated RDF and CNF line for cation (A) and anion (B) with H2SO4 in the multiple complex systems of [Bmim][SbF6] and 98 wt% concentrated sulfuric acid. (a, b) RDF and CNF of cation/anion-H2SO4; (c, d) RDF and CNF of cation/anion-H (S–O–H in the H2SO4) (color online).

  • Table 1   The Hammett acidity of the multiple complex systems

    X[ Bmim] [ SbF6 ] (wt%)

    Δδ0

    H0

    H2SO4

    80.52

    −10.063

    0.1

    80.529

    −10.075

    0.5

    80.538

    −10.087

    33

    79.678

    −9.349

    [Bmim][SbF6]

    75.785

    −7.235

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