Über die Hydrate der Salpetersäure. Eine Antwort an Herrn Hugo Erdmann

Küster, F. W.; Kremann, R.

doi:10.1002/zaac.19040410102

Cited by 39 publications

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“…There is generally good agreement, with no overall trend with temperature, though K P calculated from ∆ r H°) (Rln(K P(T) ) -Rln(K P(T r ) ) - where T r is equal to 254.63 K. Deviations of all data from the fitted equation are shown in Figure 14. Partial pressure products pHNO 3 ‚pH 2 O above nitric acid monohydrate (NAM) have been determined by Hanson and Mauersberger 9,23 and by Worsnop et al 22 Values from the fitted equations given in these studies are plotted in Figure 15, together with values calculated from the solid-phase solubilities of Kuster and Kremen 18 and Pickering, 19 and aqueous phase activities and partial pressures calculated as before. The data are consistent at the higher temperatures, but there is disagreement by up to a factor of 2 at 190 K. Forsythe and Giauque 20 have determined a melting point of 235.48 K for NAM and have also measured the heat capacity of the solid.…”

Section: Appendix IImentioning

confidence: 98%

“…e Fit of the NAT equilibrium constant (KP) uses these data, together with freezing points 18,32 (with respect to NAT) and activity coefficients and x KH(HNO3) from this study. f Fit of the NAM equilibrium constant (KP) uses these data, together with freezing points 18,32 (with respect to NAM) and activity coefficients and x KH(HNO3) presented in this work. g Fit of the NAD equilibrium constant (KP) uses these data, together with freezing points (with respect to NAD) of Ji and Petit 24 )/3.75R (A6)…”

Section: Appendix IImentioning

confidence: 99%

“…Equilibrium partial pressure products KP above HNO3‚ 3H2O(cr) (NAT). Symbols: calculated from measurements of NAT saturation in aqueous HNO3 18,19 and the revised thermodynamic model of Clegg and Brimblecombe (see Appendix I), or from pHNO3 and pH2O determined directly above solutions saturated with respect to NAT. 9,23 Lines: fitted equations from sources listed in Table 4.…”

Section: Appendix IImentioning

confidence: 99%

“…Using an estimated melting temperature of 235.34 K, and ∆ r C p terms in eq A5 calculated assuming a heat capacity of solid NAD equal to the average of NAT and NAM, the data were fitted to obtain the following expression for ln(K P [NAD]): The enthalpy change (∆rH°) for the solid h vapor equilibrium of HNO3‚3H2O(cr) (NAT), calculated from experimentally derived vapor pressure products KP. Symbols: (dot) from data for NAT saturation in aqueous HNO3 18,19 and the revised thermodynamic model of Clegg and Brimblecombe (see Appendix I), (cross) Hanson and Mauersberger 9 for aqueous solutions saturated with respect to NAT (their Figure 3), (open circle) Hanson and Mauersberger 23 for solid NAT at four temperatures (their Figure 1). Lines: (solid) Hanson and Mauersberger 23 for the NAT/NAM boundary, (dash/dot) Hanson and Mauersberger 9 for the NAT/NAM boundary, (dash/double dot) Hanson and Mauersberger 9 for the NAT/ice boundary, but using pH2O over ice calculated using the equation of Clegg and Brimblecombe, 4 (dashed) Worsnop et al 22 for solid NAT, (dotted) Hanson and Mauersberger 23 for the NAT/ice boundary, but using pH2O over ice calculated using the equation of Clegg and Brimblecombe.…”

Section: Appendix IImentioning

confidence: 99%

“…Equilibrium partial pressure products KP above HNO3‚ H2O(cr) (NAM). Symbols: (dot) calculated measurements of NAM saturation in aqueous HNO318,19 and the revised thermodynamic model of Clegg and Brimblecombe (see Appendix I), (plus) from pHNO3 and pH2O directly determined above solutions saturated with respect to NAM 9,23. Lines: (solid) Hanson and Mauersberger23 for the NAT/NAM boundary, (dash/dot) Hanson and Mauersberger 9 for the NAT/NAM boundary, (dash) Worsnop et al22 for solid NAM.…”

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Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl₂ Production from Aqueous HCl and HNO₃ and Their Mixtures

1999

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Equilibrium total pressures have been measured above aqueous HNO 3 (for 7.82, 15.73, and 35.99 mol kg -1 solutions from 294.6 to 224.7 K) and aqueous HCl (9.45 and 10.51 mol kg -1 , from 289.4 to 199.5 K) using a capacitance manometer. Equilibrium partial pressures of the acids have also been determined, by mass spectrometry, from 274.8 to 234.6 K for both HCl solutions, and from 265.0 to 240.1 K for 15.73 mol kg -1 HNO 3 . Results are generally consistent with model predictions, though with small (∼10%) systematic deviations for the total pressure measurements over aqueous HCl at about 220 K. Mixtures of HCl-HNO 3 -H 2 O composition yielded measured total pressures orders of magnitude greater than predicted for the gases H 2 O, HNO 3 , and HCl. Mass spectrometric determinations and equilibrium thermodynamic calculations suggest that Cl 2 and NOCl were produced by the reaction: 4H + (aq) + NO 3 -(aq) + 3Cl -(aq) h NOCl (aq) + Cl 2(aq) + 2H 2 O (l) , which is known to occur in aqua regia (a mixture of concentrated hydrochloric and nitric acids). Calculations for aqueous solutions of stratospheric aerosol composition suggest, purely on equilibrium grounds (and neglecting kinetics), that the reaction could be a source of active chlorine in the stratosphere. The correlation of Clegg and Brimblecombe (J. Phys. Chem. 1990, 94, 5369-5380; and 1994, 96, 6854) of the thermodynamic properties of aqueous HNO 3 activities has been revised, and vapor pressure products (for the reaction HNO 3 ‚nH 2 O (cr) h HNO 3(g) + nH 2 O (g) , where 1ene3) assessed from literature studies. The activity product for the reaction HNO 3 ‚2H 2 O (cr) h H + (aq) + NO 3 -(aq) + 2H 2 O (l) has also been determined. The model of Carslaw et al. (J. Phys. Chem. 1995, 99, 11557-11574) has been revised for the solubility of HBr in aqueous H 2 SO 4 to stratospheric temperatures.

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Section: Appendix IImentioning

confidence: 98%

Section: Appendix IImentioning

confidence: 99%

Section: Appendix IImentioning

confidence: 99%

Section: Appendix IImentioning

confidence: 99%

mentioning

confidence: 99%

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Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl₂ Production from Aqueous HCl and HNO₃ and Their Mixtures

1999

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Fortschritte der theoretischen Elektrochemie im Jahre 1904

Abel¹

1905

Angewandte Chemie

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Über die Einwirkung von nitrosen Gasen und Sauerstoff auf Wasser

Foerster

Koch

1908

Angewandte Chemie

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Bekanntlich befassen sich auI3er unserer Normal-Eichungskommission auch das belgische Bureau national des poids et mesures, das englische National Physical Laboratory und das Bureau of Standards der Vereinigten Staaten mit der Priifung chemischer MeDgerate. Das amerikanisohe Institut hat nun seine Bestimmungen von 1904 und 1906 unterm 15. Mai d. J. erganzt und ebgeiindert. Die wichtigsten sollen hier kurz hervorgehoben werden. Die Gcrate miissen vor ihrer Justierung 24 Stunden auf ca. 400' erwiirmt und dann fein gekiihlt seineine Forderung, die unsere N.-E.-Kommission nur fur Pyknometer stellt. Der Querschnitt soll iiberall kreisformig sein. Flachgedriickte, ovale Formen, wie sie bei uns geeicht werden, sind also nicht zulassig. Ebensowenig iibrigens Gerate mit Schellbachstreifen. Letzteres durchaus mit Recht, denn da die Marken bei ungeteilten Geraten rings herum, bei geteilten mindestens auf die €Elf& des Rohrumfangs gezogen werden miissen, so ist die Vermeidung der Paralhse besser gesichert als durch den Streifen. Gasanalytische Gerlite, ferner Gerate mit Prozentteilung, Pyknometer, sowie Pipetten und Biiretten auf EinguB sind nicht zugelassen. Ebenso erhalten Vollpipetten mit zwei Marken den ,,Test" nicht, wohl weil sie in bezug auf die Genauigkeit und Bequemlichkeit des Gebrauchs denen mit einer Marke nachstehen. Wenn auch Biiretten rnit 8 ) Vgl. besonders R. L u t h e r , X. physikal. Chem. 34, 488 (1900); 36, 391 (1901).

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Über die Hydrate der Salpetersäure. Eine Antwort an Herrn Hugo Erdmann

Cited by 39 publications

References 0 publications

Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl₂ Production from Aqueous HCl and HNO₃ and Their Mixtures

Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl₂ Production from Aqueous HCl and HNO₃ and Their Mixtures

Fortschritte der theoretischen Elektrochemie im Jahre 1904

Über die Einwirkung von nitrosen Gasen und Sauerstoff auf Wasser

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Über die Hydrate der Salpetersäure. Eine Antwort an Herrn Hugo Erdmann

Cited by 39 publications

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Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl2 Production from Aqueous HCl and HNO3 and Their Mixtures

Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl2 Production from Aqueous HCl and HNO3 and Their Mixtures

Fortschritte der theoretischen Elektrochemie im Jahre 1904

Über die Einwirkung von nitrosen Gasen und Sauerstoff auf Wasser

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Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl₂ Production from Aqueous HCl and HNO₃ and Their Mixtures

Equilibrium Partial Pressures, Thermodynamic Properties of Aqueous and Solid Phases, and Cl₂ Production from Aqueous HCl and HNO₃ and Their Mixtures