DOI: 10.1063/1.1724166. Statistical Mechanics of Multimolecular Adsorption II. Localized and Mobile Adsorption and Absorption

Statistical Mechanics of Multimolecular Adsorption II. Localized and Mobile Adsorption and Absorption

10.1063/1.1724166

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

It is shown that the transition from localized to mobile adsorption (in the first adsorbed layer) takes place at rather low temperatures for potential barriers of around 1000 cal./mole or less, so that localized physical adsorption should be a very rare phenomenon at the temperatures usually employed in adsorption experiments. Since the BET (and Langmuir) isotherm actually assumes localized adsorption, a new approximate isotherm equation is derived here on the basis of a mobile first layer obeying a two-dimensional van der Waals' equation. This isotherm is in semiquantitative agreement with the two-dimensional phase changes observed by Jura and co-workers, and by earlier workers, at very low pressures. The localized-mobile transition in the absorption of hydrogen by metals is mentioned briefly. The relationships between (1) the two-dimensional equation of state of a monolayer, (2) the adsorption isotherm of the monolayer, and (3) the ordinary three-dimensional equation of state of the gas being adsorbed are discussed in some detail.

Authors 1

Terrell L. Hill (first)

References 24 Referenced 236

{'key': '2024020812482250500_r1'}
{'key': '2024020812482250500_r1a'}
{'key': '2024020812482250500_r2'}
{'key': '2024020812482250500_r3'}
{'key': '2024020812482250500_r4'}
10.1063/1.1750058 / J. Chem. Phys. (1937)
10.1063/1.1723744 / J. Chem. Phys. (1942)
10.1039/tf9393501247 / Trans. Faraday Soc. (1939)
{'key': '2024020812482250500_r6'}
{'key': '2024020812482250500_r7'}
10.1017/S0305004100013359 / Proc. Camb. Phil. Soc. (1935)
10.1063/1.1724129 / J. Chem. Phys. (1946)
10.1039/tf9454100450 / Trans. Faraday Soc. (1945)
10.1063/1.1723989 / J. Chem. Phys. (1945)
10.1039/tf9454100450 / Trans. Faraday Soc. (1945)
{'key': '2024020812482250500_r12', 'first-page': '132', 'volume': '163A', 'year': '1937', 'journal-title': 'Proc. Roy. Soc.'} / Proc. Roy. Soc. (1937)
{'key': '2024020812482250500_r14', 'first-page': '175', 'volume': 'A147', 'year': '1934', 'journal-title': 'Proc. Roy. Soc.'} / Proc. Roy. Soc. (1934)
{'key': '2024020812482250500_r15'}
{'key': '2024020812482250500_r16'}
10.1021/j150373a012 / J. Phys. Chem. (1936)
{'key': '2024020812482250500_r18', 'first-page': '189', 'volume': 'B28', 'year': '1935', 'journal-title': 'Zeits. f. Physik. Chemie'} / Zeits. f. Physik. Chemie (1935)
{'key': '2024020812482250500_r19', 'first-page': '53', 'volume': '163A', 'year': '1937', 'journal-title': 'Proc. Roy. Soc.'} / Proc. Roy. Soc. (1937)
10.1063/1.1724111 / J. Chem. Phys. (1946)
{'key': '2024020812482250500_r21'}

Dates

Type	When
Created	20 years, 7 months ago (Jan. 5, 2005, 7:16 p.m.)
Deposited	1 year, 6 months ago (Feb. 8, 2024, 7:48 a.m.)
Indexed	3 weeks, 2 days ago (Aug. 6, 2025, 8:30 a.m.)
Issued	79 years, 1 month ago (July 1, 1946)
Published	79 years, 1 month ago (July 1, 1946)
Published Print	79 years, 1 month ago (July 1, 1946)

Funders 0

None

BibTeX

@article{Hill_1946, title={Statistical Mechanics of Multimolecular Adsorption II. Localized and Mobile Adsorption and Absorption}, volume={14}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1724166}, DOI={10.1063/1.1724166}, number={7}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Hill, Terrell L.}, year={1946}, month=jul, pages={441–453} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        6
      ]
    ],
    "date-time": "2025-08-06T12:30:58Z",
    "timestamp": 1754483458082
  },
  "reference-count": 24,
  "publisher": "AIP Publishing",
  "issue": "7",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        1946,
        7,
        1
      ]
    ]
  },
  "abstract": "<jats:p>It is shown that the transition from localized to mobile adsorption (in the first adsorbed layer) takes place at rather low temperatures for potential barriers of around 1000 cal./mole or less, so that localized physical adsorption should be a very rare phenomenon at the temperatures usually employed in adsorption experiments. Since the BET (and Langmuir) isotherm actually assumes localized adsorption, a new approximate isotherm equation is derived here on the basis of a mobile first layer obeying a two-dimensional van der Waals' equation. This isotherm is in semiquantitative agreement with the two-dimensional phase changes observed by Jura and co-workers, and by earlier workers, at very low pressures. The localized-mobile transition in the absorption of hydrogen by metals is mentioned briefly. The relationships between (1) the two-dimensional equation of state of a monolayer, (2) the adsorption isotherm of the monolayer, and (3) the ordinary three-dimensional equation of state of the gas being adsorbed are discussed in some detail.</jats:p>",
  "DOI": "10.1063/1.1724166",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2005,
        1,
        6
      ]
    ],
    "date-time": "2005-01-06T00:16:33Z",
    "timestamp": 1104970593000
  },
  "page": "441-453",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 236,
  "title": "Statistical Mechanics of Multimolecular Adsorption II. Localized and Mobile Adsorption and Absorption",
  "prefix": "10.1063",
  "volume": "14",
  "author": [
    {
      "given": "Terrell L.",
      "family": "Hill",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Department of Chemistry, University of Rochester, Rochester, New York"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024020812482250500_r1"
    },
    {
      "key": "2024020812482250500_r1a"
    },
    {
      "key": "2024020812482250500_r2"
    },
    {
      "key": "2024020812482250500_r3"
    },
    {
      "key": "2024020812482250500_r4"
    },
    {
      "key": "2024020812482250500_r4a",
      "doi-asserted-by": "crossref",
      "first-page": "469",
      "DOI": "10.1063/1.1750058",
      "volume": "5",
      "year": "1937",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020812482250500_r4b",
      "doi-asserted-by": "crossref",
      "first-page": "428",
      "DOI": "10.1063/1.1723744",
      "volume": "10",
      "year": "1942",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020812482250500_r5",
      "doi-asserted-by": "crossref",
      "first-page": "1247",
      "DOI": "10.1039/tf9393501247",
      "volume": "35",
      "year": "1939",
      "journal-title": "Trans. Faraday Soc."
    },
    {
      "key": "2024020812482250500_r6"
    },
    {
      "key": "2024020812482250500_r7"
    },
    {
      "key": "2024020812482250500_r8",
      "doi-asserted-by": "crossref",
      "first-page": "260",
      "DOI": "10.1017/S0305004100013359",
      "volume": "31",
      "year": "1935",
      "journal-title": "Proc. Camb. Phil. Soc."
    },
    {
      "key": "2024020812482250500_r9",
      "doi-asserted-by": "crossref",
      "first-page": "263",
      "DOI": "10.1063/1.1724129",
      "volume": "14",
      "year": "1946",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020812482250500_r9a",
      "doi-asserted-by": "crossref",
      "first-page": "450",
      "DOI": "10.1039/tf9454100450",
      "volume": "41",
      "year": "1945",
      "journal-title": "Trans. Faraday Soc."
    },
    {
      "key": "2024020812482250500_r10",
      "doi-asserted-by": "crossref",
      "first-page": "535",
      "DOI": "10.1063/1.1723989",
      "volume": "13",
      "year": "1945",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020812482250500_r11",
      "doi-asserted-by": "crossref",
      "first-page": "450",
      "DOI": "10.1039/tf9454100450",
      "volume": "41",
      "year": "1945",
      "journal-title": "Trans. Faraday Soc."
    },
    {
      "key": "2024020812482250500_r12",
      "first-page": "132",
      "volume": "163A",
      "year": "1937",
      "journal-title": "Proc. Roy. Soc."
    },
    {
      "key": "2024020812482250500_r14",
      "first-page": "175",
      "volume": "A147",
      "year": "1934",
      "journal-title": "Proc. Roy. Soc."
    },
    {
      "key": "2024020812482250500_r15"
    },
    {
      "key": "2024020812482250500_r16"
    },
    {
      "key": "2024020812482250500_r17",
      "doi-asserted-by": "crossref",
      "first-page": "523",
      "DOI": "10.1021/j150373a012",
      "volume": "40",
      "year": "1936",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024020812482250500_r18",
      "first-page": "189",
      "volume": "B28",
      "year": "1935",
      "journal-title": "Zeits. f. Physik. Chemie"
    },
    {
      "key": "2024020812482250500_r19",
      "first-page": "53",
      "volume": "163A",
      "year": "1937",
      "journal-title": "Proc. Roy. Soc."
    },
    {
      "key": "2024020812482250500_r20",
      "doi-asserted-by": "crossref",
      "first-page": "117",
      "DOI": "10.1063/1.1724111",
      "volume": "14",
      "year": "1946",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020812482250500_r21"
    }
  ],
  "container-title": "The Journal of Chemical Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/14/7/441/18794107/441_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/14/7/441/18794107/441_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        8
      ]
    ],
    "date-time": "2024-02-08T12:48:34Z",
    "timestamp": 1707396514000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/14/7/441/192197/Statistical-Mechanics-of-Multimolecular-Adsorption"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1946,
        7,
        1
      ]
    ]
  },
  "references-count": 24,
  "journal-issue": {
    "issue": "7",
    "published-print": {
      "date-parts": [
        [
          1946,
          7,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.1724166",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1946,
        7
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1946,
        7,
        1
      ]
    ]
  }
}