bose_1972#
T. K. Bose, J. S. Sochanski and R. H. Cole, “Dielectric and Pressure Virial Coefficients of Imperfect Gases. V. Octopole Moments of CH4 and CF4”, J. Chem. Phys. 57, 3592 (1972)
Source record · Catalogue · Review register
DOI: 10.1063/1.1678813
Source kind: measurement
Recorded technique: Static dielectric constants of CH4 (and CF4) from three-terminal parallel-plate capacitance cells and a decade transformer bridge (Orcutt and Cole 1967; Sutter and Cole 1970). B_eps and C_eps from the cyclic expansion technique (Sutter and Cole): f = (eps - 1)/(eps + 2) at densities in the accurately known ratio R = d_(i+3)/d_i, Delta f_i = f_i - R^-1 f_(i+3) fitted as a polynomial in f_i (Eq. 3), giving B_eps/A_eps^2 and the f_i^3 coefficient; A_eps and B_eps - A_eps B_p from a quadratic fit of f against P/RT at known pressures below 14 atm (Eqs. 1-2). At 6.6, 49 and 100 degrees C (Table I: 279.8, 322.5, 373.4 K), 1-100 atm. Matheson research-grade CH4: CO2 < 10 ppm, O2 6 ppm, N2 19 ppm, C2H6 34 ppm, C3H8 < 5 ppm (mass spectrometry) (pp. 2-3).
Materials in structured entries: CH4
Dataset quantities: molar_refractivity, refractivity_virial_coefficient
Contents: 8 datasets; 0 formulas.
Curation notes#
Identity checked against the first page (pdf page 1 is the publisher’s cover; journal p. 3592 is pdf page 2). Page numbers below are pdf pages.
WHAT THE VALUES ARE. f = (eps - 1)/(eps + 2) = A_eps d + B_eps d^2 + C_eps d^3 + ... (Eq. 1, d the molar density): A_eps is the static (audio-frequency) molar polarization, for non-polar CH4 the static polarizability, electronic plus the vibrational (‘atomic’) part; B_eps and C_eps are the STATIC DIELECTRIC second and third virial coefficients, not the optical refractivity virials. B_eps = B_ind + B_or (p. 3): B_or, the orientation polarization from the dipole induced in one molecule by the octopole moment of the other (Eq. 4), varies as 1/T; from B_eps against 1/T (Fig. 3) the authors derive B_ind = 2.5 cm^6 mol^-2 for CH4 (‘necessarily somewhat crude and uncertain’, about one-third of B_eps) and the octopole moment Omega = 3.0e-34 esu (CF4: 4.4e-34), with Lennard-Jones 12-6 parameters eps_0/k = 137 K, sigma_0 = 3.88 Angstrom (pp. 3-4); ‘trusting them to within, say 20 %’ (p. 5). So the B_eps here are orientation-dominated and exceed the optical B_R: they are stored as refractivity_virial_coefficient (order 2, and C_eps order 3) at infinite wavelength, use = check, never as an optical virial.
Uncertainty: ‘Derived values of A_eps, B_eps, and C_eps are given in Table I, the error figures being three standard deviations from the least squares fit’ (p. 3); stored as ‘3 sigma’. Fig. 3’s error bars are also three standard deviations.
Text (p. 3): ‘The values of A_eps from this work which we consider best are 6.541 +- 0.003 cm^3 mol^-1 for CH4 and 9.678 +- 0.003 cm^3 mol^-1 for CF4, corresponding to polarizabilities 2.593e-24 cm^3 for CH4 and 3.838e-24 cm^3 for CF4’ (6.541 = the 322.5 K value and near the three-temperature mean 6.541; 3 A_eps/(4 pi N_A) = 2.5928e-24 cm^3, checked 2026-09-26). Earlier values cited by Maryott and Buckley: 6.53 (CH4); 9.7, 9.73, 10.1 (CF4). The best CH4 value is entered inline (A_eps_best_CH4).
Not extracted: CF4 (not a curated species): A_eps 9.678 +- 0.002, 9.679 +- 0.004, 9.690 +- 0.002; B_eps 11.35 +- 0.44, 10.54 +- 0.64, 9.17 +- 0.75; C_eps -836 +- 92, -764 +- 218, -735 +- 237 at 279.8, 322.5, 373.4 K (Table I); B_ind(CF4) = 3.5. Table II, the pressure second virial coefficients -B_p (cm^3 mol^-1) from the low-pressure dielectric data (errors three standard deviations, p. 3) with values interpolated from Dymond and Smith (1969): CH4 52.9 +- 1.4 (lit. 50.9), 35.8 +- 2.3 (34.8), 21.8 +- 1.0 (21.0); CF4 104.6 +- 1.7 (105.0), 74.0 +- 1.4 (70.9), 43.0 +- 1.0 (43.4) at the three temperatures: an equation-of-state quantity with no optmat quantity. The octopole moments and the octopole-octopole correction (_1B_OmegaOmega = 0.1 cm^6 mol^-2 for CH4 at 6.6 degrees C, p. 4) are not optical quantities.
Reproductions: achtermann_1991’s B_eps_bose_1972_279.8_CH4, _322.5_CH4 and _373.4_CH4 (its Table III, Ref. 45) reprint this paper’s B_eps digit for digit; hohm_2013 cites it (its Ref. 173) in the CH4 dielectric mean.
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
bose_1972/A_eps_CH4#
{
"id": "A_eps_CH4",
"material": "CH4",
"file": "CH4/bose_1972__A_eps_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"includes": "electronic + vibrational static polarizability (row = temperature, K)"
}
}
Table I A_eps (cm^3 mol^-1) of CH4 at 279.8, 322.5, 373.4 K (rows = temperature, K): the static (audio-frequency) molar polarization, the electronic plus vibrational static polarizability of non-polar CH4 (the vibrational part is about 0.09 cm^3/mol, HITRAN’s 0.24 au). Rises by 0.006 (0.09 %) from 279.8 to 373.4 K, 1.7 times the combined three-sigma errors; as the slope A_tau of schmidt_2003’s Eq. (9) that is 0.0175 cm^3/mol, the ‘A_tau ~ 17e-3’ Schmidt and Moldover attribute to this paper (their p. 22; their own 0.006 to 0.011). A check on the static limit (its use is decided at review).
bose_1972/A_eps_best_CH4#
{
"id": "A_eps_best_CH4",
"material": "CH4",
"table": "text",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"includes": "electronic + vibrational static polarizability"
}
}
1 inline points in the source record.
p. 3: ‘The values of A_eps from this work which we consider best are 6.541 +- 0.003 cm^3 mol^-1 for CH4’, corresponding to 2.593e-24 cm^3. The authors’ choice from Table I (the 322.5 K value; the three-temperature mean is also 6.541): not independent of A_eps_CH4. No temperature is attached. Error level as Table I’s (three standard deviations).
bose_1972/B_eps_279.8_CH4#
{
"id": "B_eps_279.8_CH4",
"material": "CH4",
"file": "CH4/bose_1972__B_eps_279.8_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"order": 2,
"temperature_k": 279.8
}
}
Table I B_eps = 8.14 +- 0.29 cm^6 mol^-2 at 279.8 K: the STATIC DIELECTRIC second virial coefficient, B_ind + B_or with the octopole-induced orientation term B_or (about two-thirds by the authors’ B_ind = 2.5). Not the optical refractivity virial B_R: a check only (B_eps - B_R measures B_or).
bose_1972/B_eps_322.5_CH4#
{
"id": "B_eps_322.5_CH4",
"material": "CH4",
"file": "CH4/bose_1972__B_eps_322.5_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"order": 2,
"temperature_k": 322.5
}
}
Table I B_eps = 7.29 +- 0.32 cm^6 mol^-2 at 322.5 K: static dielectric, as B_eps_279.8_CH4.
bose_1972/B_eps_373.4_CH4#
{
"id": "B_eps_373.4_CH4",
"material": "CH4",
"file": "CH4/bose_1972__B_eps_373.4_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"order": 2,
"temperature_k": 373.4
}
}
Table I B_eps = 6.75 +- 0.29 cm^6 mol^-2 at 373.4 K: static dielectric, as B_eps_279.8_CH4.
bose_1972/C_eps_279.8_CH4#
{
"id": "C_eps_279.8_CH4",
"material": "CH4",
"file": "CH4/bose_1972__C_eps_279.8_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "refractivity_virial_coefficient",
"unit": "cm9/mol3",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"order": 3,
"temperature_k": 279.8
}
}
Table I C_eps = -297 +- 48 cm^9 mol^-3 at 279.8 K (the header’s unit extracts as ‘cm9 mol-8’; the image prints mol^-3): the static dielectric third virial coefficient, from the f_i^3 term of the cyclic-expansion fit (Eq. 3) and the quadratic low-pressure fit. Not an optical C_R: a check only.
bose_1972/C_eps_322.5_CH4#
{
"id": "C_eps_322.5_CH4",
"material": "CH4",
"file": "CH4/bose_1972__C_eps_322.5_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "refractivity_virial_coefficient",
"unit": "cm9/mol3",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"order": 3,
"temperature_k": 322.5
}
}
Table I C_eps = -268 +- 50 cm^9 mol^-3 at 322.5 K: static dielectric, as C_eps_279.8_CH4.
bose_1972/C_eps_373.4_CH4#
{
"id": "C_eps_373.4_CH4",
"material": "CH4",
"file": "CH4/bose_1972__C_eps_373.4_CH4.csv",
"table": "tbl_36d8a70060d0",
"quantity": "refractivity_virial_coefficient",
"unit": "cm9/mol3",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"order": 3,
"temperature_k": 373.4
}
}
Table I C_eps = -238 +- 48 cm^9 mol^-3 at 373.4 K: static dielectric, as C_eps_279.8_CH4.
Formulas#
No formulas are recorded.
Corrections#
No dataset errata are recorded in this source record.
Formula corrections, where recorded, appear with their formulas above. Curation notes may also discuss corrections or unresolved interpretation. Consult the review register for the checks and decisions.