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 `__ · :doc:`Catalogue ` · :doc:`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 \(6\.643 and 11\.322 cm^3/mol, fit/\ default models, computed 2026\-09\-25\), 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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ .. code-block:: text { "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 :doc:`review register ` for the checks and decisions.