buckingham_1974#
A. D. Buckingham and C. Graham, “The density dependence of the refractivity of gases”, Proc. R. Soc. London A 337, 275 (1974)
Source record · Catalogue · Review register
Source kind: measurement
Recorded technique: Differential (double-decompression) polarization interferometry: a Dyson-type polarization interferometer with a Spectra-Physics He-Ne laser (lambda_0 = 633.0 nm in vacuo), a reference cell and two matched sample cells (EN 58B stainless-steel tubes 43 cm long, i.d. 1.16 cm, double traverse); gas at about 5 x 10^5 Pa (SF6 2.5 x 10^5 Pa) in one sample cell is expanded into the other, then the remaining half into the evacuated first (Eqs. 16-19); the rotation of the analyser nulls the phase change to better than 1e-4 fringe; cell distortion corrected (Eqs. 23-26, Table 2). A_n from fringe counting on filling (Eq. 27) with the pressure from a mercury manometer (+-40 Pa) and densities from Dymond and Smith’s second virial coefficients (Eq. 29). Water jacket about 299 K (+-0.05 K) (pp. 280-286).
Materials in structured entries: Ar, CH4, CO2, N2, Ne, SF6
Dataset quantities: molar_refractivity, refractivity_virial_coefficient
Contents: 20 datasets; 0 formulas.
Curation notes#
Identity: VALIDATED_WITH_WARNINGS (a JSTOR reprint; pdf page 1 is the JSTOR cover, pdf page 2 the first page: Proc. R. Soc. Lond. A 337, 275 (1974), received 10 August 1973). Page numbers are journal pages (pdf page + 273). CITATION NOTE: the volume is 337 (No. 1609, 19 March 1974), as the library, vukovic_1996 and the JSTOR cover print; st_arnaud_1979, burns_1986, achtermann_1991 and hohm_1990 cite it as ‘Proc. R. Soc. A 336, 275’.
DEFINITIONS (Eqs. 3, 11, 13-15): R_m = (n^2 - 1)/(n^2 + 2)/rho = A_R + B_R rho + ..., (n - 1)/rho = A_n + B_n rho + ...; A_R = 2A_n/3, B_R = 2B_n/3 - A_n^2/9. Units: 10^6 A_R in m^3/mol = cm^3/mol, 10^12 B_R in m^6/mol^2 = cm^6/mol^2 (Table 5’s B_R header prints ‘m^6 mol^-3’, a misprint; the uncertainty columns print mol^-2).
B_R (Table 5, p. 288): ‘An estimated uncertainty in B_R is quoted in addition to the standard deviation ... the sum of three uncertainties, namely the standard deviation, the variation in B_R for +-30 % error in the correction for cell distortion, and an uncertainty +-B_Delta in B_R due to drift’ (p. 286): taken as sigma (level not stated; a sum, so conservative). Adsorption could add up to 3.5 % of the CO2 phase change (p. 284). Mean temperatures 299-300 K. The classical Silberstein-Kirkwood B_F (Eq. 35, Lennard-Jones parameters from Hirschfelder, Curtiss and Bird) agrees ‘for Ar and CH4, but poor for the other gases’ (p. 289).
A_R IS HIGH: the Table 5 A_R lie 0.10-0.40 % above the curated dispersion at 633.0 nm (fit/<gas> default models, computed 2026-09-25): Ne 1.003 / 1.0003, Ar 4.207 / 4.1957, N2 4.460 / 4.4461, CO2 6.650 / 6.6432, CH4 6.600 / 6.5740, SF6 11.34 / 11.3216 cm^3/mol, all positive and beyond the stated worst case (’+-0.2 % ... in the most unfavourable case, namely SF6’, p. 286) for Ne, Ar, N2 and CH4. A_R was a by-product (mercury manometer, virial densities); the A_R datasets are excluded, the B_R kept. The Landolt-Bornstein literature A_R of Table 5 (Ne 1.002, Ar 4.196, N2 4.458, CO2 6.647, CH4 6.537 and 6.576, SF6 11.409) state no wavelength and are not extracted.
TABLE 1 (the literature before this work, p. 278): the curated rows at infinite wavelength (dielectric A_eps and B_eps: He, Ne, Ar, Kr of Orcutt and Cole 1967 and their Ar values of 1965 and Johnston et al. 1960) and CO2 at 546.1 nm (Phillips 1920 via Orcutt and Cole) are orcutt_1967’s values, identical (checked 2026-09-25), and are not extracted again; Bose and Cole’s (1970) argon A_eps = 4.1397(6), B_eps = 0.72(12) at 322.9 K are extracted as reproduced. Rows over 447.1-667.8 nm (Michels and Botzen, Michels et al., Michels and Hamers; Ar, N2, CO2) have no single wavelength and are not extracted (as in orcutt_1967). Non-curated gases skipped.
TABLE 4 (representative single double-decompression runs, B_R Ne -0.03, Ar 2.11, N2 1.01, CO2 3.8, CH4 7.14, SF6 30.6) is not extracted: Table 5 is the summary. REPRODUCTIONS OF THIS PAPER in the curated set: st_arnaud_1976 and st_arnaud_1979 (Table 5 values with the ‘estimated uncertainty’), and, under the citation string with volume 336, burns_1986, achtermann_1991, hohm_1990 and vukovic_1996 (volume 337): their reproduced_from can now name buckingham_1974.
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
buckingham_1974/A_R_Ne#
{
"id": "A_R_Ne",
"material": "Ne",
"file": "Ne/buckingham_1974__A_R_Ne.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "excluded"
}
Table 5, 10^6 A_R = 1.003 m^3/mol at 633.0 nm (He-Ne, in vacuo), about 299 K. EXCLUDED: 0.27 % above the curated value at 633.0 nm (1.0003), one of six systematically high A_R (source notes).
buckingham_1974/B_R_Ne#
{
"id": "B_R_Ne",
"material": "Ne",
"file": "Ne/buckingham_1974__B_R_Ne.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "primary",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 300.0
}
}
Table 5, 10^12 B_R (m^6/mol^2) at 633.0 nm, mean temperature 300 K, from the double-decompression B_n through Eq. (14); sigma is the table’s ‘estimated uncertainty’ (standard deviation + distortion-correction + drift terms, summed).
buckingham_1974/B_F_theory_Ne#
{
"id": "B_F_theory_Ne",
"material": "Ne",
"file": "Ne/buckingham_1974__B_F_theory_Ne.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 300.0
}
}
Table 5 ‘calculated B_F’: the classical fluctuation (dipole-induced dipole) term of Eq. (35) with the Lennard-Jones potential (Hirschfelder, Curtiss and Bird) and the measured A_R; filed at the measurement wavelength. A check.
buckingham_1974/A_R_Ar#
{
"id": "A_R_Ar",
"material": "Ar",
"file": "Ar/buckingham_1974__A_R_Ar.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "excluded"
}
Table 5, 10^6 A_R = 4.207 m^3/mol at 633.0 nm (He-Ne, in vacuo), about 299 K. EXCLUDED: 0.27 % above the curated value at 633.0 nm (4.1957), one of six systematically high A_R (source notes).
buckingham_1974/B_R_Ar#
{
"id": "B_R_Ar",
"material": "Ar",
"file": "Ar/buckingham_1974__B_R_Ar.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "primary",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 299.0
}
}
Table 5, 10^12 B_R (m^6/mol^2) at 633.0 nm, mean temperature 299 K, from the double-decompression B_n through Eq. (14); sigma is the table’s ‘estimated uncertainty’ (standard deviation + distortion-correction + drift terms, summed).
buckingham_1974/B_F_theory_Ar#
{
"id": "B_F_theory_Ar",
"material": "Ar",
"file": "Ar/buckingham_1974__B_F_theory_Ar.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 299.0
}
}
Table 5 ‘calculated B_F’: the classical fluctuation (dipole-induced dipole) term of Eq. (35) with the Lennard-Jones potential (Hirschfelder, Curtiss and Bird) and the measured A_R; filed at the measurement wavelength. A check.
buckingham_1974/A_R_N2#
{
"id": "A_R_N2",
"material": "N2",
"file": "N2/buckingham_1974__A_R_N2.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "excluded"
}
Table 5, 10^6 A_R = 4.460 m^3/mol at 633.0 nm (He-Ne, in vacuo), about 299 K. EXCLUDED: 0.31 % above the curated value at 633.0 nm (4.4461), one of six systematically high A_R (source notes).
buckingham_1974/B_R_N2#
{
"id": "B_R_N2",
"material": "N2",
"file": "N2/buckingham_1974__B_R_N2.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "primary",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 299.0
}
}
Table 5, 10^12 B_R (m^6/mol^2) at 633.0 nm, mean temperature 299 K, from the double-decompression B_n through Eq. (14); sigma is the table’s ‘estimated uncertainty’ (standard deviation + distortion-correction + drift terms, summed).
buckingham_1974/B_F_theory_N2#
{
"id": "B_F_theory_N2",
"material": "N2",
"file": "N2/buckingham_1974__B_F_theory_N2.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 299.0
}
}
Table 5 ‘calculated B_F’: the classical fluctuation (dipole-induced dipole) term of Eq. (35) with the Lennard-Jones potential (Hirschfelder, Curtiss and Bird) and the measured A_R; filed at the measurement wavelength. A check.
buckingham_1974/A_R_CO2#
{
"id": "A_R_CO2",
"material": "CO2",
"file": "CO2/buckingham_1974__A_R_CO2.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "excluded"
}
Table 5, 10^6 A_R = 6.650 m^3/mol at 633.0 nm (He-Ne, in vacuo), about 299 K. EXCLUDED: 0.10 % above the curated value at 633.0 nm (6.6432), one of six systematically high A_R (source notes).
buckingham_1974/B_R_CO2#
{
"id": "B_R_CO2",
"material": "CO2",
"file": "CO2/buckingham_1974__B_R_CO2.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "primary",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 299.0
}
}
Table 5, 10^12 B_R (m^6/mol^2) at 633.0 nm, mean temperature 299 K, from the double-decompression B_n through Eq. (14); sigma is the table’s ‘estimated uncertainty’ (standard deviation + distortion-correction + drift terms, summed).
buckingham_1974/B_F_theory_CO2#
{
"id": "B_F_theory_CO2",
"material": "CO2",
"file": "CO2/buckingham_1974__B_F_theory_CO2.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 299.0
}
}
Table 5 ‘calculated B_F’: the classical fluctuation (dipole-induced dipole) term of Eq. (35) with the Lennard-Jones potential (Hirschfelder, Curtiss and Bird) and the measured A_R; filed at the measurement wavelength. A check.
buckingham_1974/A_R_CH4#
{
"id": "A_R_CH4",
"material": "CH4",
"file": "CH4/buckingham_1974__A_R_CH4.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "excluded"
}
Table 5, 10^6 A_R = 6.600 m^3/mol at 633.0 nm (He-Ne, in vacuo), about 299 K. EXCLUDED: 0.40 % above the curated value at 633.0 nm (6.5740), one of six systematically high A_R (source notes).
buckingham_1974/B_R_CH4#
{
"id": "B_R_CH4",
"material": "CH4",
"file": "CH4/buckingham_1974__B_R_CH4.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "primary",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 299.0
}
}
Table 5, 10^12 B_R (m^6/mol^2) at 633.0 nm, mean temperature 299 K, from the double-decompression B_n through Eq. (14); sigma is the table’s ‘estimated uncertainty’ (standard deviation + distortion-correction + drift terms, summed).
buckingham_1974/B_F_theory_CH4#
{
"id": "B_F_theory_CH4",
"material": "CH4",
"file": "CH4/buckingham_1974__B_F_theory_CH4.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 299.0
}
}
Table 5 ‘calculated B_F’: the classical fluctuation (dipole-induced dipole) term of Eq. (35) with the Lennard-Jones potential (Hirschfelder, Curtiss and Bird) and the measured A_R; filed at the measurement wavelength. A check.
buckingham_1974/A_R_SF6#
{
"id": "A_R_SF6",
"material": "SF6",
"file": "SF6/buckingham_1974__A_R_SF6.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "excluded"
}
Table 5, 10^6 A_R = 11.34 m^3/mol at 633.0 nm (He-Ne, in vacuo), about 299 K. EXCLUDED: 0.16 % above the curated value at 633.0 nm (11.3216), one of six systematically high A_R (source notes).
buckingham_1974/B_R_SF6#
{
"id": "B_R_SF6",
"material": "SF6",
"file": "SF6/buckingham_1974__B_R_SF6.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "primary",
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 299.0
}
}
Table 5, 10^12 B_R (m^6/mol^2) at 633.0 nm, mean temperature 299 K, from the double-decompression B_n through Eq. (14); sigma is the table’s ‘estimated uncertainty’ (standard deviation + distortion-correction + drift terms, summed).
buckingham_1974/B_F_theory_SF6#
{
"id": "B_F_theory_SF6",
"material": "SF6",
"file": "SF6/buckingham_1974__B_F_theory_SF6.csv",
"table": "tbl_0cfd7fe493cd",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 299.0
}
}
Table 5 ‘calculated B_F’: the classical fluctuation (dipole-induced dipole) term of Eq. (35) with the Lennard-Jones potential (Hirschfelder, Curtiss and Bird) and the measured A_R; filed at the measurement wavelength. A check.
buckingham_1974/A_eps_bose_cole_1970_Ar#
{
"id": "A_eps_bose_cole_1970_Ar",
"material": "Ar",
"file": "Ar/buckingham_1974__A_eps_bose_cole_1970_Ar.csv",
"table": "tbl_8d9922d080a7",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"bose_1970",
"H. G. Sutter, Specialist Periodical Reports, in Dielectric and related molecular processes (ed. M. Davies), p. 65 (Chemical Society, London, 1972)"
],
"uncertainty": {
"column": true,
"level": "3 sigma"
}
}
Table 1, ‘Bose & Cole 1970; Sutter 1972’, 322.9 K, infinite wavelength, in parentheses: the dielectric (static) A_eps of argon, 4.1397(6) cm^3/mol: bose_1970’s Table II value at 49.7 degrees C, 4.1397 +- 0.0006, digit for digit (re-pointed 2026-09-27; Sutter 1972 is not in the library). The original’s errors are three standard deviations: level corrected to ‘3 sigma’.
buckingham_1974/B_eps_bose_cole_1970_Ar#
{
"id": "B_eps_bose_cole_1970_Ar",
"material": "Ar",
"file": "Ar/buckingham_1974__B_eps_bose_cole_1970_Ar.csv",
"table": "tbl_8d9922d080a7",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"bose_1970"
],
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 322.9
}
}
Table 1, ‘Bose & Cole 1970; Sutter 1972’, 322.9 K: the second dielectric virial coefficient B_eps of argon, 0.72(12) cm^6/mol^2 (for a monatomic gas equal to the static B_R, p. 277): bose_1970’s 0.72 +- 0.12 at 49.7 degrees C, digit for digit (re-pointed 2026-09-27). The original’s errors are three standard deviations: level corrected to ‘3 sigma’.
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.