st_arnaud_1979#
J. M. St-Arnaud and T. K. Bose, “Direct determination of the intermolecular interaction contribution to the refractive index of carbon dioxide and sulfur hexafluoride”, J. Chem. Phys. 71, 4951 (1979)
Source record · Catalogue · Review register
DOI: 10.1063/1.438308
Source kind: measurement
Recorded technique: The direct expansion method of st_arnaud_1976 (two nearly equal optical cells joined by a valve, the gas expanded from one into the other, the change of the summed optical path measured by a Hewlett-Packard 5525A He-Ne interferometer at 6328 A), extended to about 80 atm; B_n from the slope of Eq. (16) (a quadratic in the summed refractivities for CO2, linear for SF6), A_R from the absolute refractive index against pressure below 12 atm (quartz Bourdon gauge calibrated against a pressure balance). Both gases at 323 K. CO2 (Union Carbide; O2 < 1, N2 < 8 ppm), SF6 research grade, 99.18 % minimum (air and CF4 the main impurities) (pp. 4951-4952).
Materials in structured entries: CO2, SF6
Dataset quantities: molar_refractivity, refractivity_virial_coefficient
Contents: 14 datasets; 0 formulas.
Curation notes#
Identity: VALIDATED_WITH_WARNINGS in the library (a caption warning); first page checked (pdf page 2: J. Chem. Phys. 71, 4951 (1979), received 4 June 1979; pdf page 1 is the publisher’s cover). The DOI is the library’s. Page numbers are journal pages (pdf page + 4949).
DEFINITIONS as st_arnaud_1976 (Eqs. 1, 8-11): A_R, B_R of the Lorentz-Lorenz function against molar density; the Clausius-Mossotti A_eps, B_eps (Eq. 2) at low frequency, with B_eps = B_FIR + B_IR + B_R (Eq. 3). ‘Our estimated error for A_R, B_R, and B_P is three standard deviations’ (p. 4953).
A_R (6328 A, 323 K): CO2 6.658 +- 0.021, SF6 11.348 +- 0.021 cm^3/mol, both 0.23 % above the curated dispersion at 632.99 nm (6.643 and 11.322 cm^3/mol, fit/<gas> default models, computed 2026-09-25), within the stated 3 sigma. A_eps - A_R gives the ‘atomic’ (vibrational) polarizability: 9 % of the total for CO2, 31 % for SF6 (Eqs. 17, 18; alpha_atom 2.74 +- 0.10 and 20.59 +- 0.15 x 10^-25 cm^3, derived, not extracted).
B_R (6328 A, 323 K): CO2 3.3 +- 3.6, SF6 36.0 +- 1.8 cm^6/mol^2; the classical DID theory (Eq. 20, Lennard-Jones 6-12 with sigma = 3.819 A, epsilon/k = 218.8 K for CO2; 7-28 with 4.68 A, 439 K for SF6) gives 6.9 and 24.8. C_R of CO2 was fitted but is ‘rather inaccurate’ and not printed. B_eps - B_R agrees with B_FIR + B_IR (Table III: CO2 47.4 +- 4.5 against 49.0 +- 5; SF6 27.3 +- 4.6 against 24.73).
Not extracted: B_P (Table II, a density virial, and the literature B_P); Table I’s Landolt-Bornstein A_R (SF6 11.41, CO2 6.647; footnote a, no wavelength or temperature) and Timoshenko et al. and Kholodov et al.’s CO2 A_R 6.687 and B_R 4.6 (243-363 K, Refs. 7, 8, no wavelength); Orcutt and Cole’s CO2 B_R 5.3 at 323 K (Ref. 9 = orcutt_1967, which quotes 5.3 +- 0.9 as a fit of Michels and Hamers’s data averaged over 4471-6678 A: no single wavelength); the derived alpha columns; B_FIR and B_IR (no quantity: SF6 0.53 (Ref. 27) and 24.2 (Ref. 3, calculated); CO2 48 +- 5 (Ref. 28, 333 K) and 1.0).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
st_arnaud_1979/A_R_this_work_CO2#
{
"id": "A_R_this_work_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__A_R_this_work_CO2.csv",
"table": "tbl_42f95d223f73",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "primary",
"uncertainty": {
"column": true,
"level": "3 sigma"
}
}
Table I ‘This work’, 323 K, 6328 A (He-Ne, air wavelength): A_R from the Lorentz-Lorenz function against P/RT below 12 atm (Fig. 3, the intercept); three standard deviations. 0.23 % above the curated dispersion at 632.99 nm (source notes).
st_arnaud_1979/A_R_buckingham_graham_1974_CO2#
{
"id": "A_R_buckingham_graham_1974_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__A_R_buckingham_graham_1974_CO2.csv",
"table": "tbl_42f95d223f73",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "reproduced",
"reproduced_from": [
"buckingham_1974"
]
}
Table I, Ref. 11 (Buckingham and Graham 1974), 298 K: printed without uncertainty; 6328 A as for their CH4 (st_arnaud_1976).
st_arnaud_1979/A_eps_dielectric_CO2#
{
"id": "A_eps_dielectric_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__A_eps_dielectric_CO2.csv",
"table": "tbl_42f95d223f73",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"bose_1970"
],
"uncertainty": {
"column": true,
"level": "3 sigma"
}
}
Table I, Ref. 4 (= bose_1970, re-pointed 2026-09-27), listed at 298 K: the static dielectric A_eps (Clausius-Mossotti), which includes the vibrational (‘atomic’) polarizability: 9 % above A_R here. Not an optical value. 7.350 +- 0.006 is the original’s 49.7 degrees C (322.85 K) value, not a 298 K one (the original has 7.358 +- 0.002 at 29.4 degrees C); the original’s errors are three standard deviations: level corrected to ‘3 sigma’.
st_arnaud_1979/B_R_this_work_CO2#
{
"id": "B_R_this_work_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__B_R_this_work_CO2.csv",
"table": "tbl_4533c14b419a",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "primary",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 323.0
}
}
Table II ‘This work’, 323 K, 6328 A: the direct expansion measurement; three standard deviations. A quadratic fit of Eq. (16) (with C_R); the value is barely significant (3.3 +- 3.6).
st_arnaud_1979/B_R_theory_CO2#
{
"id": "B_R_theory_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__B_R_theory_CO2.csv",
"table": "tbl_4533c14b419a",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 323.0
}
}
Table II ‘Theory’, 323 K: the classical point-dipole (DID) value of Eq. (20) with a Lennard-Jones 6-12 potential (sigma = 3.819 A, epsilon/k = 218.8 K; footnote b); no wavelength (filed at ‘inf’). A check.
st_arnaud_1979/B_R_buckingham_graham_1974_CO2#
{
"id": "B_R_buckingham_graham_1974_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__B_R_buckingham_graham_1974_CO2.csv",
"table": "tbl_4533c14b419a",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "reproduced",
"reproduced_from": [
"buckingham_1974"
],
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 298.0
}
}
Table II, Ref. 11 (Buckingham and Graham 1974), 298 K, 6328 A.
st_arnaud_1979/B_eps_dielectric_CO2#
{
"id": "B_eps_dielectric_CO2",
"material": "CO2",
"file": "CO2/st_arnaud_1979__B_eps_dielectric_CO2.csv",
"table": "tbl_4e565abf97f8",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"bose_1970"
],
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 323.0
}
}
Table III, Ref. 4 (footnote c; = bose_1970, re-pointed 2026-09-27), 323 K: the second DIELECTRIC virial coefficient B_eps (static), which contains B_FIR and B_IR besides B_R (Eq. 3). The original prints 50.7 +- 0.93 at 49.7 degrees C (checked); its errors are three standard deviations: level corrected to ‘3 sigma’.
st_arnaud_1979/A_R_this_work_SF6#
{
"id": "A_R_this_work_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__A_R_this_work_SF6.csv",
"table": "tbl_42f95d223f73",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "primary",
"uncertainty": {
"column": true,
"level": "3 sigma"
}
}
Table I ‘This work’, 323 K, 6328 A (He-Ne, air wavelength): A_R from the Lorentz-Lorenz function against P/RT below 12 atm (Fig. 3, the intercept); three standard deviations. 0.23 % above the curated dispersion at 632.99 nm (source notes).
st_arnaud_1979/A_R_buckingham_graham_1974_SF6#
{
"id": "A_R_buckingham_graham_1974_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__A_R_buckingham_graham_1974_SF6.csv",
"table": "tbl_42f95d223f73",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "reproduced",
"reproduced_from": [
"buckingham_1974"
]
}
Table I, Ref. 11 (Buckingham and Graham 1974), 298 K: printed without uncertainty; 6328 A as for their CH4 (st_arnaud_1976).
st_arnaud_1979/A_eps_dielectric_SF6#
{
"id": "A_eps_dielectric_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__A_eps_dielectric_SF6.csv",
"table": "tbl_42f95d223f73",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"hosticka_1974"
],
"uncertainty": {
"column": true,
"level": "3 sigma"
}
}
Table I, Ref. 5 (= hosticka_1974, re-pointed 2026-09-27), listed at 298 K: the static dielectric A_eps (Clausius-Mossotti), which includes the vibrational (‘atomic’) polarizability: 31 % above A_R here. Not an optical value. 16.543 +- 0.017 is the original’s 323.3 K value (it has no 298 K measurement); its errors are three standard deviations: level corrected to ‘3 sigma’.
st_arnaud_1979/B_R_this_work_SF6#
{
"id": "B_R_this_work_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__B_R_this_work_SF6.csv",
"table": "tbl_4533c14b419a",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "primary",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 323.0
}
}
Table II ‘This work’, 323 K, 6328 A: the direct expansion measurement; three standard deviations. A linear fit of Eq. (16).
st_arnaud_1979/B_R_theory_SF6#
{
"id": "B_R_theory_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__B_R_theory_SF6.csv",
"table": "tbl_4533c14b419a",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "check",
"parameters": {
"temperature_k": 323.0
}
}
Table II ‘Theory’, 323 K: the classical point-dipole (DID) value of Eq. (20) with a generalized Lennard-Jones 7-28 potential (sigma = 4.68 A, epsilon/k = 439 K; footnote a); no wavelength (filed at ‘inf’). A check.
st_arnaud_1979/B_R_buckingham_graham_1974_SF6#
{
"id": "B_R_buckingham_graham_1974_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__B_R_buckingham_graham_1974_SF6.csv",
"table": "tbl_4533c14b419a",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "standard_air",
"use": "reproduced",
"reproduced_from": [
"buckingham_1974"
],
"uncertainty": {
"column": true,
"level": "not stated"
},
"parameters": {
"temperature_k": 298.0
}
}
Table II, Ref. 11 (Buckingham and Graham 1974), 298 K, 6328 A.
st_arnaud_1979/B_eps_dielectric_SF6#
{
"id": "B_eps_dielectric_SF6",
"material": "SF6",
"file": "SF6/st_arnaud_1979__B_eps_dielectric_SF6.csv",
"table": "tbl_4e565abf97f8",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"hosticka_1974"
],
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 323.0
}
}
Table III, Ref. 5 (footnote a; = hosticka_1974, re-pointed 2026-09-27), 323 K: the second DIELECTRIC virial coefficient B_eps (static), which contains B_FIR and B_IR besides B_R (Eq. 3). The original prints 63.31 +- 2.80 at 323.3 K (reprinted rounded, 63.3 +- 2.8); its 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.