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Oct 1989

Volume 18, Issue 4, pp. 1537-1812


A Fundamental Equation for Water Covering the Range from the Melting Line to 1273 K at Pressures up to 25 000 MPa

A. Saul and W. Wagner

J. Phys. Chem. Ref. Data 18, 1537 (1989); http://dx.doi.org/10.1063/1.555836 (28 pages) | Cited 30 times

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In order to represent the thermodynamic properties of water (H2O) over an extremely large range of temperature and pressure that is not covered by existing equations of state, a new fundamental equation has been developed. The Helmholtz function was fitted to the following kinds of experimental data: (a) pρT data, (b) thermal properties of the saturation curve (ps,ρ′,ρ″), (c) speed of sound w, (d) isobaric heat capacity cp, (e) isochoric heat capacity cv, (f) differences of the internal energy u, (g) differences of the enthalpy h, (h) Joule–Thomson coefficient μ, and (i) the isothermal throttling coefficient δT. A new statistical selection method was used to determine the final form of the equation from a ‘‘bank’’ of 630 terms which also contained functional forms that have not been previously used. This 58‐coefficient equation covers the entire fluid region from the melting line to 1273 K at pressures up to 25 000 MPa, and represents the data within their experimental accuracy also in the ‘‘difficult’’ regions below 0 °C, on the entire saturation curve, in the critical region and at very high pressures. The equation was constrained at the critical point as defined by the parameters internationally recommended by the International Association for the Properties of Steam (IAPS). Besides the 58‐coefficient equation for the entire pressure range, a 38‐coefficient equation is presented for providing a ‘‘fast’’ equation for practical and scientific calculations in the pressure range below 1000 MPa. This equation has, with the exception of the critical region, nearly the same accuracy as the 58‐coefficient equation. The quality of the new equations will be illustrated by comparing the values calculated from them with selected experimental data and with the IAPS‐84 formulation and the Scaling‐Law equation.
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64.30.-t Equations of state of specific substances
65.20.-w Thermal properties of liquids
65.40.gd Entropy

Toluene Thermophysical Properties from 178 to 800 K at Pressures to 1000 Bar

Robert D. Goodwin

J. Phys. Chem. Ref. Data 18, 1565 (1989); http://dx.doi.org/10.1063/1.555837 (72 pages) | Cited 7 times

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The thermodynamic data for toluene have been evaluated and fit to a highly constrained, nonanalytic equation of state. Comparisons of the equation with the selected PVT and derived property data are given. Extensive tables are presented providing tabular values for coexisting liquid and vapor as well as for the single phase along isobars. The equation of state and tables cover the range from the triple point (178.15 K) to 800 K, with pressures to 1000 bar.
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64.30.-t Equations of state of specific substances
65.20.-w Thermal properties of liquids
65.40.gd Entropy

Reduction Potentials of One‐Electron Couples Involving Free Radicals in Aqueous Solution

Peter Wardman

J. Phys. Chem. Ref. Data 18, 1637 (1989); http://dx.doi.org/10.1063/1.555843 (119 pages) | Cited 2 times

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Reduction of an electron acceptor (oxidant), A, or oxidation of an electron donor (reductant), A2, is often achieved stepwise via one‐electron processes involving the couples A/A⋅ or A⋅/A2 (or corresponding prototropic conjugates such as A/AH⋅ or AH⋅/AH2). The intermediate A⋅(AH⋅) is a free radical. The reduction potentials of such one‐electron couples are of value in predicting the direction or feasibility, and in some instances the rate constants, of many free‐radical reactions. Electrochemical methods have limited applicability in measuring these properties of frequently unstable species, but fast, kinetic spectrophotometry (especially pulse radiolysis) has widespread application in this area. Tables of ca. 1200 values of reduction potentials of ca. 700 one‐electron couples in aqueous solution are presented. The majority of organic oxidants listed are quinones, nitroaryl and bipyridinium compounds. Reductants include phenols, aromatic amines, indoles and pyrimidines, thiols and phenothiazines. Inorganic couples largely involve compounds of oxygen, sulfur, nitrogen and the halogens. Proteins, enzymes and metals and their complexes are excluded.
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82.50.Kx Processes caused by X-rays or γ-rays
82.30.Fi Ion-molecule, ion-ion, and charge-transfer reactions
82.30.Cf Atom and radical reactions; chain reactions; molecule-molecule reactions
82.20.Pm Rate constants, reaction cross sections, and activation energies

Photoemission Cross Sections for Atomic Transitions in the Extreme Ultraviolet due to Electron Collisions with Atoms and Molecules

P. J. M. van der Burgt, W. B. Westerveld, and J. S. Risley

J. Phys. Chem. Ref. Data 18, 1757 (1989); http://dx.doi.org/10.1063/1.555844 (49 pages) | Cited 5 times

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This article reviews experimental photoemission cross sections in the extreme ultraviolet, for transitions in excited atoms and atomic ions formed in electron collisions with atoms and molecules. A survey of the available experimental data for each investigated target gas reveals severe inconsistencies between cross sections reported by different laboratories. As almost all reported cross sections are based on relative measurements, a detailed discussion is given of the methods used for normalization of the cross sections.
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34.50.Fa Electronic excitation and ionization of atoms (including beam-foil excitation and ionization)
34.50.Gb Electronic excitation and ionization of molecules
32.30.Jc Visible and ultraviolet spectra
33.20.Ni Vacuum ultraviolet spectra

Erratum: The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C1 and C2 organic substances in SI units [J. Phys. Chem. Ref. Data 11, Suppl. 2 (1982)]

Donald D. Wagman, William H. Evans, Vivian B. Parker, Richard H. Schumm, Iva Halow, Sylvia M. Bailey, Kenneth L. Churney, and Ralph L. Nuttall

J. Phys. Chem. Ref. Data 18, 1807 (1989); http://dx.doi.org/10.1063/1.555845 (6 pages)

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Abstract Unavailable
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82.60.-s Chemical thermodynamics
65.20.-w Thermal properties of liquids
65.40.gd Entropy
99.10.Cd Errata
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