kirouac_1973#
S. Kirouac and T. K. Bose, “Dielectric and pressure virial coefficients of imperfect gases. Pure N2O”, J. Chem. Phys. 59, 3043 (1973)
Source record · Catalogue · Review register
DOI: 10.1063/1.1680442
Source kind: measurement
Recorded technique: Dielectric constants of N2O from three-terminal parallel-plate capacitance cells and a General Radio 1615A decade transformer bridge (the apparatus of Orcutt and Cole 1967 and Sutter and Cole 1970; audio frequency, static). B_eps and C_eps from the cyclic (Burnett-type) expansion technique, Delta f_i = f_i - f_{i+2}/R fitted in f_i^2 and f_i^3 (Eq. 5); A_eps and the pressure virial B_p from measurements below 14 atm, [(eps - 1)/(eps + 2)](RT/P) fitted by least squares as a polynomial in P/RT (Eq. 4), A_eps the intercept. At 6.5, 30.1 and 75.1 degrees C. Matheson research-grade N2O with O2 600 ppm, N2 2000 ppm, NO-NO2 0.5 ppm, CO2 3 ppm, chlorides 1 ppm, water 35 ppm, Cl-C4 0.2 ppm (mass spectrometry) (pp. 2-3).
Materials in structured entries: N2O
Dataset quantities: molar_refractivity, polarizability, refractivity_virial_coefficient
Contents: 5 datasets; 0 formulas.
Curation notes#
Page numbers are the library pdf pages (pdf page 1 is the publisher’s cover; journal p. 3043 is pdf page 2).
WHAT A_eps INCLUDES. (eps - 1)/((eps + 2) d) = A_eps + B_eps d + C_eps d^2 (Eq. 1, d the molar density), and for a polar molecule A_eps = (4 pi N_0/3)(alpha_0 + mu_0^2/3kT) (Eq. 2, p. 2): A_eps is the static molar polarization, the static polarizability alpha_0 (electronic plus the vibrational, ‘atomic’, part: the bridge is far below the infrared bands) PLUS the orientation polarization of N2O’s permanent dipole. The paper separates them by the Debye plot of A_eps against 1/T (Fig. 2; ‘The intercept in Fig. 2 measures 4/3 pi N_0 (alpha_0 + mu_0^2/3kT)’, p. 3): ‘the mean values of alpha_0 and mu_0 are 3.03e-24 cm^3 and 0.18 D’ (p. 3; abstract), the dipole ‘in excellent agreement with the microwave value 0.167 D of Shulman, Dailey and Townes’. It does not split alpha_0 into its electronic and vibrational parts. Check (2026-09-25): a straight line A_eps = a + b/T through Table I gives a = 7.660 cm^3/mol (alpha_0 = 3.036e-24 cm^3) and mu_0 = 0.1805 D, reproducing the printed 3.03e-24 and 0.18 D to rounding; with Table I’s +- as one sigma, a has +-0.039 cm^3/mol (0.5 %), strongly anticorrelated with mu_0. The orientation term is 0.55-0.66 cm^3/mol (7-8 % of A_eps) over 6.5-75.1 degrees C.
Uncertainty: Table I’s +- are not described; the only statement is ‘Our estimated error is 3 times the standard deviation given by a least square fit’ (p. 3), written after the discussion of B_p. Stored as ‘3 sigma’ on that reading (TC-152).
B_eps (Discussion, pp. 3-5): B_eps = B_ind + B_or; B_or (dipole-dipole and quadrupole-induced orientation terms) dominates; from B_eps against 1/T the authors derive B_ind = (0 +- 2) cm^6/mol^2 (‘We shall therefore consider that all the measured B_eps is essentially the contribution of B_or’, p. 4). So B_eps is an orientation (static) quantity with no optical counterpart: the refractivity virial of N2O at optical frequencies is not measured here.
Not extracted: C_eps (Table I: -1275.7 +- 1060.5, -1656.0 +- 597.9, -2055.7 +- 995.0 cm^9/mol^3 at 6.5, 30.1, 75.1 degrees C; no quantity); Table II’s pressure virial -B_p (cm^3/mol: this work 146.4 +- 1.5, 119.7 +- 1.2, 101.2 +- 4.0; theoretical 152, 127, 96; literature 149, 126, 98; no quantity); Table III’s corrections to B_or and Table IV’s quadrupole moments (the result: 3.4e-26 esu cm^2); Lennard-Jones parameters eps_0/k = 235.5 K, R_0 = 3.802e-8 cm (Spurling and Mason).
Recorded bibliographic identity status: VALIDATED_WITH_WARNINGS. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
kirouac_1973/A_eps#
{
"id": "A_eps",
"material": "N2O",
"file": "N2O/kirouac_1973__A_eps.csv",
"table": "tbl_18fe8b762246",
"quantity": "molar_refractivity",
"unit": "cm3/mol",
"abscissa_unit": "nm",
"use": "check",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"includes": "electronic + vibrational static polarizability + orientation polarization mu_0^2/3kT (row = temperature, K)"
}
}
Table I A_eps (cm^3/mol) at 6.5, 30.1, 75.1 degrees C (rows: 279.65, 303.25, 348.25 K), static (capacitance bridge). A CHECK, NOT A POLARIZABILITY: it includes the orientation polarization (4 pi N_0/3) mu_0^2/3kT, 0.55-0.66 cm^3/mol (7-8 %) by the authors’ own mu_0 = 0.18 D, besides the electronic and vibrational static polarizability; converting it to a per-molecule alpha overstates alpha by that much. Uncertainty as printed, level read as 3 sigma (see the source notes).
kirouac_1973/alpha_0#
{
"id": "alpha_0",
"material": "N2O",
"table": "text",
"quantity": "polarizability",
"unit": "cm3",
"scale": 1e-24,
"abscissa_unit": "nm",
"use": "check"
}
1 inline points in the source record.
p. 3 (and abstract): alpha_0 = 3.03e-24 cm^3 (polarizability volume), the static polarizability from the Debye analysis of A_eps(T) (intercept of A_eps against 1/T, with mu_0 = 0.18 D): electronic plus vibrational, without the orientation term. No uncertainty is stated; a straight line through Table I gives +-0.5 % (one sigma, if the +- are one sigma), strongly anticorrelated with mu_0 (the microwave 0.167 D quoted by the authors would raise alpha_0 by 1.2 %). A check, derived from A_eps.
kirouac_1973/B_eps_279.65#
{
"id": "B_eps_279.65",
"material": "N2O",
"file": "N2O/kirouac_1973__B_eps_279.65.csv",
"table": "tbl_18fe8b762246",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"use": "excluded",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 279.65
}
}
Table I B_eps = 36.06 +- 1.72 cm^6/mol^2 at 6.5 degrees C. Excluded: the dielectric second virial coefficient of a polar, quadrupolar molecule is orientation-dominated (B_ind = 0 +- 2 by the authors, p. 4); it is not the optical refractivity virial. Uncertainty level read as 3 sigma.
kirouac_1973/B_eps_303.25#
{
"id": "B_eps_303.25",
"material": "N2O",
"file": "N2O/kirouac_1973__B_eps_303.25.csv",
"table": "tbl_18fe8b762246",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"use": "excluded",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 303.25
}
}
Table I B_eps = 32.35 +- 1.34 cm^6/mol^2 at 30.1 degrees C. Excluded, as B_eps_279.65.
kirouac_1973/B_eps_348.25#
{
"id": "B_eps_348.25",
"material": "N2O",
"file": "N2O/kirouac_1973__B_eps_348.25.csv",
"table": "tbl_18fe8b762246",
"quantity": "refractivity_virial_coefficient",
"unit": "cm6/mol2",
"abscissa_unit": "nm",
"use": "excluded",
"uncertainty": {
"column": true,
"level": "3 sigma"
},
"parameters": {
"temperature_k": 348.25
}
}
Table I B_eps = 28.08 +- 2.56 cm^6/mol^2 at 75.1 degrees C. Excluded, as B_eps_279.65.
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.