Skip to main content

Advertisement

SpringerLink
Log in

NMR Studies on Solution Structures of Methanol and Ethanol Saturated with CO2

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

2H and 17O NMR relaxation times, T 1(2H) and T 1(17O), and 2H NMR chemical shifts, δ(2H), in CO2-saturated CD3OD and C2D5OD solutions were measured at 313.2 K over the pressure range up to ~6 MPa. The rotational correlation times, τ r, of the CD and OD axes within CD3OD and C2D5OD molecules and the CO axis within the CO2 molecule were determined from T 1(2H) and T 1(17O), and the magnetic susceptibility-corrected chemical shifts, δ corr, were derived from δ(2H). The differences in τ r and δ corr observed between the two alcohol systems: τ r and δ corr of OD in C2D5OD, decreased rapidly with increasing CO2 concentration, while those of OD in CD3OD remained almost unchanged at mole fractions of CO2, \( x_{\text CO_{2}} \), lower than ~0.25 and then slightly decreased at higher \( x_{\text CO_{2}} \). The hydrogen bonding structure in C2D5OD was found to be gradually broken down by CO2 dissolution. On the other hand, in CD3OD, it has been revealed that the hydrogen bonding structure can persist at \( x_{\text CO_{2}} \) < ~0.25 but then collapses at higher \( x_{\text CO_{2}} \).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Akien, G.R., Poliakoff, M.: A critical look at reactions in class I and II gas-expanded liquids using CO2 and other gases. Green Chem. 11, 1083–1100 (2009)

    Article  CAS  Google Scholar 

  2. Hutchenson, K.W., Scurto, A.M., Subramaniam, B. (eds.): Gas-Expanded Liquids and Near-Critical Media, ACS Symposium Series 1006. American Chemical Society, Washington, DC (2009)

    Google Scholar 

  3. Sih, R., Dehghani, F., Foster, N.R.: Viscosity measurements on gas expanded liquid systems–methanol and carbon dioxide. J. Supercrit. Fluids 41, 148–157 (2007)

    Article  CAS  Google Scholar 

  4. Sih, R., Armenti, M., Mammucatri, R., Dehghani, F., Foster, N.R.: Viscosity measurements on saturated gas expanded liquid systems–ethanol and carbon dioxide. J. Supercrit. Fluids 43, 460–468 (2008)

    Article  CAS  Google Scholar 

  5. Aida, T., Aizawa, T., Kanakubo, M., Nanjo, H.: Relation between volume expansion and hydrogen bond networks for CO2–alcohol mixtures at 40°C. J. Phys. Chem. B 114, 13628–13636 (2010)

    Article  CAS  Google Scholar 

  6. Saharay, M., Balasubramanian, S.: Electron donor-acceptor interactions in ethanol–CO2 mixtures: an ab initio molecular dynamics study of supercritical carbon dioxide. J. Phys. Chem. B 110, 3782–3790 (2006)

    Article  CAS  Google Scholar 

  7. Kanakubo, M., Umecky, T., Kawanami, H., Aizawa, T., Ikushima, Y., Masuda, Y.: Determination of anisotropic solvation structure of octafluorotoluene in supercritical carbon dioxide by means of solvent-induced 19F NMR chemical shift. Chem. Phys. Lett. 338, 95–100 (2001)

    Article  CAS  Google Scholar 

  8. Kanakubo, M., Umecky, T., Liew, C.C., Aizawa, T., Hatakeda, K., Ikushima, Y.: High-pressure NMR studies on solvation structure in supercritical carbon dioxide. Fluid Phase Equilib. 194–197, 859–868 (2002)

    Article  Google Scholar 

  9. Kanakubo, M., Umecky, T., Raveendran, P., Ebina, T., Ikushima, Y.: High-pressure 19F NMR measurements of a series of fluorinated benzenes in supercritical carbon dioxide. J. Solution Chem. 33, 863–874 (2004)

    Article  CAS  Google Scholar 

  10. Umecky, T., Kanakubo, M., Ikushima, Y.: 9Be NMR relaxation measurements of bis(acetylacetonato)beryllium(II) in liquid and supercritical carbon dioxide: a clear evidence of near-critical solvation effect on rotational correlation time. J. Phys. Chem. B 106, 11114–11119 (2002)

    Article  CAS  Google Scholar 

  11. Umecky, T., Kanakubo, M., Ikushima, Y.: Experimental determination of reorientational correlation time of CO2 over a wide range of density and temperature. J. Phys. Chem. B 107, 12003–12008 (2003)

    Article  CAS  Google Scholar 

  12. Umecky, T., Kanakubo, M., Ikushima, Y.: Fluorination effect on rotational correlation times of tris(β-diketonato)aluminum(III) in CO2 by 27Al NMR relaxation measurements. J. Phys. Chem. B 115, 10622–10630 (2011)

    Article  CAS  Google Scholar 

  13. Tsukahara, T., Harada, M., Tomiyasu, H., Ikeda, Y.: NMR studies on effects of temperature, pressure, and fluorination on structures and dynamics of alcohols in liquid and supercritical states. J. Phys. Chem. A 112, 9657–9664 (2008)

    Article  CAS  Google Scholar 

  14. Debye, P.: Polar Molecules. Dover, New York (1929)

    Google Scholar 

  15. Mizuno, K., Ochi, T., Shimada, S., Nishimura, Y., Maeda, S., Koga, Y.: Magnetic susceptibility of aqueous tert-butanol. Phys. Chem. Chem. Phys. 1, 133–135 (1999)

    Article  CAS  Google Scholar 

  16. Mizuno, K., Tamiya, Y., Mekata, M.: External double reference method to study concentration and temperature dependences of chemical shifts determined on a unified scale. Pure Appl. Chem. 76, 105–114 (2004)

    Article  CAS  Google Scholar 

  17. Lide, D.R. (ed.): CRC Handbook of Chemistry and Physics, 86th edn. CRC Press, Boca Raton (2005)

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Graduate School of Science and Engineering, Saga University, Honjo-machi, Saga, 840-8502, Japan

    T. Umecky & T. Takamuku

  2. National Institute of Advanced Industrial Science and Technology, 4-2-1 Nigatake, Miyagino-ku, Sendai, 983-8551, Japan

    T. Aida, T. Makino, T. Aizawa & M. Kanakubo

Authors
  1. T. Umecky
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. T. Takamuku
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. T. Aida
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. T. Makino
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. T. Aizawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. M. Kanakubo
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to T. Umecky or M. Kanakubo.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 23 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Umecky, T., Takamuku, T., Aida, T. et al. NMR Studies on Solution Structures of Methanol and Ethanol Saturated with CO2 . J Solution Chem 43, 1539–1549 (2014). https://doi.org/10.1007/s10953-014-0222-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-014-0222-z

Keywords

Search

Navigation