DOI: 10.1063/1.438628. Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity

Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity

10.1063/1.438628

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The thermal conductivities of H2O and D2O vapors were measured in a modified thick hot wire cell between 358 and 386 K at pressures ranging from 100 to 1000 Torr. Analysis of the data indicates that molecular association to form a dimeric species is the main source of enhancement of the thermal conductivity of both vapors. The enthalpy and entropy of association of the H2O dimer are −3.59 kcal mol−1 and −18.59 cal deg−1 mol−1, respectively. The enthalpy and entropy of association of the D2O dimer are −3.66 kcal mol−1 and −18.67 cal deg−1 mol−1, respectively. The measured enthalpy of association of the H2O dimer is in agreement with recently reported ab initio molecular orbital calculations on the H2O dimer. The entropies of association of the H2O and D2O dimers are calculated theoretically and are found to be in agreement with the measured values.

Bibliography

Curtiss, L. A., Frurip, D. J., & Blander, M. (1979). Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity. The Journal of Chemical Physics, 71(6), 2703â2711.

Authors 3

L. A. Curtiss (first)
D. J. Frurip (additional)
M. Blander (additional)

References 51 Referenced 656

10.1063/1.1746606 / J. Chem. Phys. (1947)
10.1063/1.1669687 / J. Chem. Phys. (1968)
10.1063/1.1670494 / J. Chem. Phys. (1968)
10.1063/1.1671800 / J. Chem. Phys. (1969)
10.1039/tf9494500974 / Trans. Faraday Soc. (1949)
10.1021/ja01137a061 / J. Am. Chem. Soc. (1952)
10.1038/221143a0 / Nature (1969)
{'key': '2024020918254439100_r6'}
10.1063/1.433651 / J. Chem. Phys. (1977)
10.1021/j100524a012 / J. Phys. Chem. (1977)
10.1021/ja00469a013 / J. Am. Chem. Soc. (1978)
10.1021/j100513a004 / J. Phys. Chem. (1978)
10.1016/0009-2614(78)85290-7 / Chem. Phys. Lett. (1978)
{'key': '2024020918254439100_r12', 'first-page': '711', 'volume': '38', 'year': '1952', 'journal-title': 'Bull. Acad. R. Belg. (Cl.Sc.)'} / Bull. Acad. R. Belg. (Cl.Sc.) (1952)
10.1063/1.1730650 / J. Chem. Phys. (1959)
10.1063/1.1696657 / J. Chem. Phys. (1965)
10.1063/1.1743596 / J. Chem. Phys. (1957)
10.1063/1.1730841 / J. Chem. Phys. (1960)
10.1063/1.1743284 / J. Chem. Phys. (1957)
{'key': '2024020918254439100_r14'}
{'key': '2024020918254439100_r15'}
10.1063/1.1732130 / J. Chem. Phys. (1961)
{'key': '2024020918254439100_r17', 'first-page': '303', 'volume': 'XIX', 'year': '1953', 'journal-title': 'Physica'} / Physica (1953)
10.1063/1.1744257 / J. Chem. Phys. (1958)
10.1063/1.1724352 / Phys. Fluids (1958)
{'key': '2024020918254439100_r19'}
{'key': '2024020918254439100_r20'}
{'key': '2024020918254439100_r21'}
{'key': '2024020918254439100_r22', 'first-page': '1521', 'volume': '62', 'year': '1970', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1970)
10.1016/0022-2852(75)90245-3 / J. Mol. Spectrosc. (1975)
10.1063/1.1743285 / J. Chem. Phys. (1957)
10.1063/1.430542 / J. Chem. Phys. (1975)
{'key': '2024020918254439100_r25a', 'first-page': '1966', 'volume': '33', 'year': '1975', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1975)
10.1016/0017-9310(67)90160-3 / Int. J. Heat Mass Transfer (1967)
{'key': '2024020918254439100_r26', 'first-page': '67', 'volume': '10', 'year': '1965', 'journal-title': 'QCPE'} / QCPE (1965)
{'key': '2024020918254439100_r26a'}
10.1021/ed042p604 / J. Chem. Educ. (1965)
10.1016/0017-9310(64)90021-3 / Int. J. Heat Mass Transfer (1964)
10.1063/1.434966 / J. Chem. Phys. (1977)
10.1063/1.1673723 / J. Chem. Phys. (1970)
10.1063/1.1730649 / J. Chem. Phys. (1959)
10.1063/1.1723708 / J. Chem. Phys. (1942)
{'key': '2024020918254439100_r33'}
{'key': '2024020918254439100_r34'}
10.1146/annurev.pc.27.100176.001401 / Ann. Rev. Phys. Chem. (1976)
{'key': '2024020918254439100_r36'}
10.1021/j100584a010 / J. Phys. Chem. (1975)
10.1063/1.1680187 / J. Chem. Phys. (1973)
10.1007/BF00549690 / Theoret. Chim. Acta (1975)
10.1063/1.432402 / J. Chem. Phys. (1976)
10.1063/1.1681463 / J. Chem. Phys. (1974)

Dates

Type	When
Created	22 years, 5 months ago (Feb. 27, 2003, 4:39 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 3:29 p.m.)
Indexed	2 days ago (Aug. 19, 2025, 6:17 a.m.)
Issued	45 years, 11 months ago (Sept. 15, 1979)
Published	45 years, 11 months ago (Sept. 15, 1979)
Published Print	45 years, 11 months ago (Sept. 15, 1979)

Funders 0

None

BibTeX

@article{Curtiss_1979, title={Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity}, volume={71}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.438628}, DOI={10.1063/1.438628}, number={6}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Curtiss, L. A. and Frurip, D. J. and Blander, M.}, year={1979}, month=sep, pages={2703–2711} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        19
      ]
    ],
    "date-time": "2025-08-19T10:17:28Z",
    "timestamp": 1755598648288
  },
  "reference-count": 51,
  "publisher": "AIP Publishing",
  "issue": "6",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        1979,
        9,
        15
      ]
    ]
  },
  "abstract": "<jats:p>The thermal conductivities of H2O and D2O vapors were measured in a modified thick hot wire cell between 358 and 386 K at pressures ranging from 100 to 1000 Torr. Analysis of the data indicates that molecular association to form a dimeric species is the main source of enhancement of the thermal conductivity of both vapors. The enthalpy and entropy of association of the H2O dimer are \u22123.59 kcal\u2009mol\u22121 and \u221218.59 cal\u2009deg\u22121\u2009mol\u22121, respectively. The enthalpy and entropy of association of the D2O dimer are \u22123.66 kcal\u2009mol\u22121 and \u221218.67 cal\u2009deg\u22121\u2009mol\u22121, respectively. The measured enthalpy of association of the H2O dimer is in agreement with recently reported ab\u2008initio molecular orbital calculations on the H2O dimer. The entropies of association of the H2O and D2O dimers are calculated theoretically and are found to be in agreement with the measured values.</jats:p>",
  "DOI": "10.1063/1.438628",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2003,
        2,
        27
      ]
    ],
    "date-time": "2003-02-27T21:39:21Z",
    "timestamp": 1046381961000
  },
  "page": "2703-2711",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 656,
  "title": "Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity",
  "prefix": "10.1063",
  "volume": "71",
  "author": [
    {
      "given": "L. A.",
      "family": "Curtiss",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Chemical Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439"
        }
      ]
    },
    {
      "given": "D. J.",
      "family": "Frurip",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Chemical Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439"
        }
      ]
    },
    {
      "given": "M.",
      "family": "Blander",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Chemical Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024020918254439100_r1",
      "doi-asserted-by": "crossref",
      "first-page": "602",
      "DOI": "10.1063/1.1746606",
      "volume": "15",
      "year": "1947",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r2",
      "doi-asserted-by": "crossref",
      "first-page": "3805",
      "DOI": "10.1063/1.1669687",
      "volume": "48",
      "year": "1968",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r2a",
      "doi-asserted-by": "crossref",
      "first-page": "2839",
      "DOI": "10.1063/1.1670494",
      "volume": "49",
      "year": "1968",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r2b",
      "doi-asserted-by": "crossref",
      "first-page": "4345",
      "DOI": "10.1063/1.1671800",
      "volume": "51",
      "year": "1969",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r3",
      "doi-asserted-by": "crossref",
      "first-page": "974",
      "DOI": "10.1039/tf9494500974",
      "volume": "45",
      "year": "1949",
      "journal-title": "Trans. Faraday Soc."
    },
    {
      "key": "2024020918254439100_r4",
      "doi-asserted-by": "crossref",
      "first-page": "4439",
      "DOI": "10.1021/ja01137a061",
      "volume": "74",
      "year": "1952",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024020918254439100_r5",
      "doi-asserted-by": "crossref",
      "first-page": "143",
      "DOI": "10.1038/221143a0",
      "volume": "221",
      "year": "1969",
      "journal-title": "Nature"
    },
    {
      "key": "2024020918254439100_r6"
    },
    {
      "key": "2024020918254439100_r7",
      "doi-asserted-by": "crossref",
      "first-page": "177",
      "DOI": "10.1063/1.433651",
      "volume": "66",
      "year": "1977",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r8",
      "doi-asserted-by": "crossref",
      "first-page": "857",
      "DOI": "10.1021/j100524a012",
      "volume": "81",
      "year": "1977",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024020918254439100_r9",
      "doi-asserted-by": "crossref",
      "first-page": "79",
      "DOI": "10.1021/ja00469a013",
      "volume": "100",
      "year": "1978",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024020918254439100_r10",
      "doi-asserted-by": "crossref",
      "first-page": "2555",
      "DOI": "10.1021/j100513a004",
      "volume": "82",
      "year": "1978",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024020918254439100_r11",
      "doi-asserted-by": "crossref",
      "first-page": "575",
      "DOI": "10.1016/0009-2614(78)85290-7",
      "volume": "54",
      "year": "1978",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024020918254439100_r12",
      "first-page": "711",
      "volume": "38",
      "year": "1952",
      "journal-title": "Bull. Acad. R. Belg. (Cl.Sc.)"
    },
    {
      "key": "2024020918254439100_r12a",
      "doi-asserted-by": "crossref",
      "first-page": "1545",
      "DOI": "10.1063/1.1730650",
      "volume": "31",
      "year": "1959",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r12b",
      "doi-asserted-by": "crossref",
      "first-page": "4166",
      "DOI": "10.1063/1.1696657",
      "volume": "43",
      "year": "1965",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r13",
      "doi-asserted-by": "crossref",
      "first-page": "1636",
      "DOI": "10.1063/1.1743596",
      "volume": "26",
      "year": "1957",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r13a",
      "doi-asserted-by": "crossref",
      "first-page": "1005",
      "DOI": "10.1063/1.1730841",
      "volume": "32",
      "year": "1960",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r13b",
      "doi-asserted-by": "crossref",
      "first-page": "274",
      "DOI": "10.1063/1.1743284",
      "volume": "26",
      "year": "1957",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r14"
    },
    {
      "key": "2024020918254439100_r15"
    },
    {
      "key": "2024020918254439100_r16",
      "doi-asserted-by": "crossref",
      "first-page": "1676",
      "DOI": "10.1063/1.1732130",
      "volume": "35",
      "year": "1961",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r17",
      "first-page": "303",
      "volume": "XIX",
      "year": "1953",
      "journal-title": "Physica"
    },
    {
      "key": "2024020918254439100_r18",
      "doi-asserted-by": "crossref",
      "first-page": "1000",
      "DOI": "10.1063/1.1744257",
      "volume": "28",
      "year": "1958",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r18a",
      "doi-asserted-by": "crossref",
      "first-page": "361",
      "DOI": "10.1063/1.1724352",
      "volume": "1",
      "year": "1958",
      "journal-title": "Phys. Fluids"
    },
    {
      "key": "2024020918254439100_r19"
    },
    {
      "key": "2024020918254439100_r20"
    },
    {
      "key": "2024020918254439100_r21"
    },
    {
      "key": "2024020918254439100_r22",
      "first-page": "1521",
      "volume": "62",
      "year": "1970",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r23",
      "doi-asserted-by": "crossref",
      "first-page": "1",
      "DOI": "10.1016/0022-2852(75)90245-3",
      "volume": "55",
      "year": "1975",
      "journal-title": "J. Mol. Spectrosc."
    },
    {
      "key": "2024020918254439100_r24",
      "doi-asserted-by": "crossref",
      "first-page": "282",
      "DOI": "10.1063/1.1743285",
      "volume": "26",
      "year": "1957",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r25",
      "doi-asserted-by": "crossref",
      "first-page": "903",
      "DOI": "10.1063/1.430542",
      "volume": "62",
      "year": "1975",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r25a",
      "first-page": "1966",
      "volume": "33",
      "year": "1975",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r25b",
      "doi-asserted-by": "crossref",
      "first-page": "409",
      "DOI": "10.1016/0017-9310(67)90160-3",
      "volume": "10",
      "year": "1967",
      "journal-title": "Int. J. Heat Mass Transfer"
    },
    {
      "key": "2024020918254439100_r26",
      "first-page": "67",
      "volume": "10",
      "year": "1965",
      "journal-title": "QCPE"
    },
    {
      "key": "2024020918254439100_r26a"
    },
    {
      "key": "2024020918254439100_r27",
      "doi-asserted-by": "crossref",
      "first-page": "604",
      "DOI": "10.1021/ed042p604",
      "volume": "42",
      "year": "1965",
      "journal-title": "J. Chem. Educ."
    },
    {
      "key": "2024020918254439100_r28",
      "doi-asserted-by": "crossref",
      "first-page": "33",
      "DOI": "10.1016/0017-9310(64)90021-3",
      "volume": "7",
      "year": "1964",
      "journal-title": "Int. J. Heat Mass Transfer"
    },
    {
      "key": "2024020918254439100_r29",
      "doi-asserted-by": "crossref",
      "first-page": "1144",
      "DOI": "10.1063/1.434966",
      "volume": "67",
      "year": "1977",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r30",
      "doi-asserted-by": "crossref",
      "first-page": "4858",
      "DOI": "10.1063/1.1673723",
      "volume": "52",
      "year": "1970",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r31",
      "doi-asserted-by": "crossref",
      "first-page": "1531",
      "DOI": "10.1063/1.1730649",
      "volume": "31",
      "year": "1959",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r32",
      "doi-asserted-by": "crossref",
      "first-page": "201",
      "DOI": "10.1063/1.1723708",
      "volume": "10",
      "year": "1942",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r33"
    },
    {
      "key": "2024020918254439100_r34"
    },
    {
      "key": "2024020918254439100_r35",
      "doi-asserted-by": "crossref",
      "first-page": "261",
      "DOI": "10.1146/annurev.pc.27.100176.001401",
      "volume": "27",
      "year": "1976",
      "journal-title": "Ann. Rev. Phys. Chem."
    },
    {
      "key": "2024020918254439100_r36"
    },
    {
      "key": "2024020918254439100_r37",
      "doi-asserted-by": "crossref",
      "first-page": "1794",
      "DOI": "10.1021/j100584a010",
      "volume": "79",
      "year": "1975",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024020918254439100_r38",
      "doi-asserted-by": "crossref",
      "first-page": "1325",
      "DOI": "10.1063/1.1680187",
      "volume": "59",
      "year": "1973",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r39",
      "doi-asserted-by": "crossref",
      "first-page": "249",
      "DOI": "10.1007/BF00549690",
      "volume": "36",
      "year": "1975",
      "journal-title": "Theoret. Chim. Acta"
    },
    {
      "key": "2024020918254439100_r40",
      "doi-asserted-by": "crossref",
      "first-page": "1351",
      "DOI": "10.1063/1.432402",
      "volume": "64",
      "year": "1976",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020918254439100_r41",
      "doi-asserted-by": "crossref",
      "first-page": "2929",
      "DOI": "10.1063/1.1681463",
      "volume": "60",
      "year": "1974",
      "journal-title": "J. Chem. Phys."
    }
  ],
  "container-title": "The Journal of Chemical Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/71/6/2703/18919533/2703_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/71/6/2703/18919533/2703_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        9
      ]
    ],
    "date-time": "2024-02-09T20:29:41Z",
    "timestamp": 1707510581000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/71/6/2703/443153/Studies-of-molecular-association-in-H2O-and-D2O"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1979,
        9,
        15
      ]
    ]
  },
  "references-count": 51,
  "journal-issue": {
    "issue": "6",
    "published-print": {
      "date-parts": [
        [
          1979,
          9,
          15
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.438628",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1979,
        9,
        15
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1979,
        9,
        15
      ]
    ]
  }
}