Freezing and melting of methanol in a single cylindrical pore: Dynamical supercooling and vitrification of methanol
10.1063/1.481742
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

To study the freezing/melting behavior of a confined CH3OH, we performed x-ray diffraction measurements of CH3OH confined inside the cylindrical pores of seven kinds of regular mesoporous adsorbents (MCM-41 and SBA-15) with different pore radii (r=1.2, 2.1, 2.5, 3.9, 4.5, 5.3, and 7.0 nm) as a function of temperature. The freezing/melting behavior depends markedly upon the pore size. Within the pores of r⩽3.9 nm, the confined CH3OH vitrifies on freezing. On the other hand, cooling of the CH3OH confined to the pores of r⩾4.5 nm results in crystallization of the liquid. Within the pores of r=5.3 nm, the crystallization proceeds in two steps: prefreezing first occurs and then it transforms into a crystalline solid with the same structure as that of the bulk α phase. The prefreezing temperature seems to lower steeply with decreasing pore-size and to approach the freezing temperature for the pores of r=4.5 nm. Cooling of the CH3OH confined to the pores of r=7.0 nm results in formation of a crystalline solid with the same structure as that of the bulk β phase and it does not transform into the low temperature α phase on further cooling down to 30 K, leading to the appearance of a glassy crystal with the β phase structure. A large hysteresis effect between freezing and melting is observed. A mechanism of the vitrification is discussed.

Bibliography

Morishige, K., & Kawano, K. (2000). Freezing and melting of methanol in a single cylindrical pore: Dynamical supercooling and vitrification of methanol. The Journal of Chemical Physics, 112(24), 11023–11029.

Authors 2
  1. Kunimitsu Morishige (first)
  2. Keizi Kawano (additional)
References 20 Referenced 54
  1. 10.1088/0034-4885/62/1/001 / Rep. Prog. Phys. (1999)
  2. 10.1063/1.478372 / J. Chem. Phys. (1999)
  3. 10.1021/jp991177m / J. Phys. Chem. B (1999)
  4. {'key': '2024021023095893800_r4', 'first-page': '2894', 'volume': '104', 'year': '2000', 'journal-title': 'J. Phys. Chem. B'} / J. Phys. Chem. B (2000)
  5. 10.1021/ja00053a020 / J. Am. Chem. Soc. (1992)
  6. 10.1021/ja974025i / J. Am. Chem. Soc. (1998)
  7. 10.1021/ja00091a041 / J. Am. Chem. Soc. (1994)
  8. 10.1246/bcsj.41.2586 / Bull. Chem. Soc. Jpn. (1968)
  9. 10.1021/la970079u / Langmuir (1997)
  10. 10.1021/la960354x / Langmuir (1996)
  11. 10.1107/S0365110X53001678 / Acta Crystallogr. (1953)
  12. 10.1103/PhysRevB.35.6779 / Phys. Rev. B (1987)
  13. 10.1063/1.459240 / J. Chem. Phys. (1990)
  14. 10.1103/PhysRevB.48.9021 / Phys. Rev. B (1993)
  15. 10.1007/BF00681704 / J. Low Temp. Phys. (1986)
  16. 10.1016/0039-6028(95)00728-8 / Surf. Sci. (1995)
  17. 10.1007/BF00752275 / J. Low Temp. Phys. (1995)
  18. 10.1103/PhysRevB.58.5329 / Phys. Rev. B (1998)
  19. 10.1063/1.1699435 / J. Appl. Phys. (1950)
  20. {'key': '2024021023095893800_r20', 'first-page': '29', 'volume': '57', 'year': '1965', 'journal-title': 'Ind. Eng. Chem.'} / Ind. Eng. Chem. (1965)
Dates
Type When
Created 23 years ago (July 26, 2002, 8:19 a.m.)
Deposited 1 year, 6 months ago (Feb. 10, 2024, 6:10 p.m.)
Indexed 1 year, 1 month ago (July 23, 2024, 1:52 a.m.)
Issued 25 years, 2 months ago (June 22, 2000)
Published 25 years, 2 months ago (June 22, 2000)
Published Print 25 years, 2 months ago (June 22, 2000)
Funders 0

None

@article{Morishige_2000, title={Freezing and melting of methanol in a single cylindrical pore: Dynamical supercooling and vitrification of methanol}, volume={112}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.481742}, DOI={10.1063/1.481742}, number={24}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Morishige, Kunimitsu and Kawano, Keizi}, year={2000}, month=jun, pages={11023–11029} }