On the structure selectivity of clathrate hydrates

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

We propose a strategic method to search for a new clathrate hydrate by investigating the selectivity of its crystalline structure, which has been expected to depend mostly on the guest species and less on the thermodynamic conditions. Relative stability among various morphologies is examined in terms of the chemical potential of water of clathrate hydrates in equilibrium with guest gases. This evaluation is performed by calculating the free energy of cage occupancy according to the standard statistical mechanical theory with the aid of the Yarmolyuk and Kripyakevich's rule on the Frank-Kasper type alloys to estimate the numbers of cages of various types. Thus, a comprehensive interpretation of the selectivity of crystalline structures is successfully made. We explain why two major structures are stable in most of the thermodynamic conditions and establish a relation between polymorphism of clathrate hydrate and the guest size and other parameters, thereby suggesting a way to find a new clathrate hydrate by appropriate choice of the guest species and/or the thermodynamic properties. It is found that there is a small room in the above parameter space for the other structure than the major two to be the most stable, including a new structure. In addition, simple but thorough elucidation is given for preferential formation of TS-I structure in bromine hydrate.

Original languageEnglish
Pages (from-to)8257-8265
Number of pages9
JournalJournal of Physical Chemistry B
Volume115
Issue number25
DOIs
Publication statusPublished - Jun 30 2011

Fingerprint

clathrates
Hydrates
hydrates
selectivity
Thermodynamics
Crystalline materials
Bromine
thermodynamics
Chemical potential
polymorphism
bromine
Polymorphism
Free energy
rooms
Thermodynamic properties
thermodynamic properties
Gases
free energy
Water
evaluation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

On the structure selectivity of clathrate hydrates. / Matsumoto, Masakazu; Tanaka, Hideki.

In: Journal of Physical Chemistry B, Vol. 115, No. 25, 30.06.2011, p. 8257-8265.

Research output: Contribution to journalArticle

@article{2dca078d0add4cb98e7b5adec88f334f,
title = "On the structure selectivity of clathrate hydrates",
abstract = "We propose a strategic method to search for a new clathrate hydrate by investigating the selectivity of its crystalline structure, which has been expected to depend mostly on the guest species and less on the thermodynamic conditions. Relative stability among various morphologies is examined in terms of the chemical potential of water of clathrate hydrates in equilibrium with guest gases. This evaluation is performed by calculating the free energy of cage occupancy according to the standard statistical mechanical theory with the aid of the Yarmolyuk and Kripyakevich's rule on the Frank-Kasper type alloys to estimate the numbers of cages of various types. Thus, a comprehensive interpretation of the selectivity of crystalline structures is successfully made. We explain why two major structures are stable in most of the thermodynamic conditions and establish a relation between polymorphism of clathrate hydrate and the guest size and other parameters, thereby suggesting a way to find a new clathrate hydrate by appropriate choice of the guest species and/or the thermodynamic properties. It is found that there is a small room in the above parameter space for the other structure than the major two to be the most stable, including a new structure. In addition, simple but thorough elucidation is given for preferential formation of TS-I structure in bromine hydrate.",
author = "Masakazu Matsumoto and Hideki Tanaka",
year = "2011",
month = "6",
day = "30",
doi = "10.1021/jp203478z",
language = "English",
volume = "115",
pages = "8257--8265",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - On the structure selectivity of clathrate hydrates

AU - Matsumoto, Masakazu

AU - Tanaka, Hideki

PY - 2011/6/30

Y1 - 2011/6/30

N2 - We propose a strategic method to search for a new clathrate hydrate by investigating the selectivity of its crystalline structure, which has been expected to depend mostly on the guest species and less on the thermodynamic conditions. Relative stability among various morphologies is examined in terms of the chemical potential of water of clathrate hydrates in equilibrium with guest gases. This evaluation is performed by calculating the free energy of cage occupancy according to the standard statistical mechanical theory with the aid of the Yarmolyuk and Kripyakevich's rule on the Frank-Kasper type alloys to estimate the numbers of cages of various types. Thus, a comprehensive interpretation of the selectivity of crystalline structures is successfully made. We explain why two major structures are stable in most of the thermodynamic conditions and establish a relation between polymorphism of clathrate hydrate and the guest size and other parameters, thereby suggesting a way to find a new clathrate hydrate by appropriate choice of the guest species and/or the thermodynamic properties. It is found that there is a small room in the above parameter space for the other structure than the major two to be the most stable, including a new structure. In addition, simple but thorough elucidation is given for preferential formation of TS-I structure in bromine hydrate.

AB - We propose a strategic method to search for a new clathrate hydrate by investigating the selectivity of its crystalline structure, which has been expected to depend mostly on the guest species and less on the thermodynamic conditions. Relative stability among various morphologies is examined in terms of the chemical potential of water of clathrate hydrates in equilibrium with guest gases. This evaluation is performed by calculating the free energy of cage occupancy according to the standard statistical mechanical theory with the aid of the Yarmolyuk and Kripyakevich's rule on the Frank-Kasper type alloys to estimate the numbers of cages of various types. Thus, a comprehensive interpretation of the selectivity of crystalline structures is successfully made. We explain why two major structures are stable in most of the thermodynamic conditions and establish a relation between polymorphism of clathrate hydrate and the guest size and other parameters, thereby suggesting a way to find a new clathrate hydrate by appropriate choice of the guest species and/or the thermodynamic properties. It is found that there is a small room in the above parameter space for the other structure than the major two to be the most stable, including a new structure. In addition, simple but thorough elucidation is given for preferential formation of TS-I structure in bromine hydrate.

UR - http://www.scopus.com/inward/record.url?scp=79959536886&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79959536886&partnerID=8YFLogxK

U2 - 10.1021/jp203478z

DO - 10.1021/jp203478z

M3 - Article

C2 - 21619053

AN - SCOPUS:79959536886

VL - 115

SP - 8257

EP - 8265

JO - Journal of Physical Chemistry B Materials

JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

IS - 25

ER -