Carbonate equilibria in hydrothermal systems: First ionization of carbonic acid in NaCl media to 300°C

Patterson, C. Stuart; Slocum, G.H; Busey, R. H.; Mesmer, R.E.

doi:10.1016/0016-7037(82)90320-9

Cited by 138 publications

(76 citation statements)

References 33 publications

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“…27 The major advantage of the Li and Duan 54 equation is that it includes the effect of pressure. Other studies that became available since the study of Plummer and Busenberg 27 are Patterson et al 55 and Park et al 56 Neither of these seems to agree with the well-established earlier studies to within experimental error, and were not considered here.…”

Section: -15 Iupac-nist Solubility Data Series 95-1mentioning

confidence: 63%

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 1. Introduction, Be and Mg

Visscher

Vanderdeelen

Königsberger

et al. 2012

Journal of Physical and Chemical Reference Data

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The alkaline earth carbonates are an important class of minerals. This volume compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1, the present paper, outlines the procedure adopted in this volume in detail, and presents the beryllium and magnesium carbonates. For the minerals magnesite (MgCO 3 ), nesquehonite (MgCO 3 Á3H 2 O), and lansfordite (MgCO 3 Á5H 2 O), a critical evaluation is presented based on curve fits to empirical and=or thermodynamic models. Useful side products of the compilation and evaluation of the data outlined in the introduction are new relationships for the Henry constant of CO 2 with Sechenov parameters, and for various equilibria in the aqueous phase including the dissociation constants of CO 2 (aq) and the stability constant of the ion pair MCO 0 3 ðaqÞ (M ¼ alkaline earth metal). Thermodynamic data of the alkaline earth carbonates consistent with two thermodynamic model variants are proposed. The model variant that describes the Mg 2þ ÀHCO À 3 ion interaction with Pitzer parameters was more consistent with the solubility data and with other thermodynamic data than the model variant that described the interaction with a stability constant.

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Section: -15 Iupac-nist Solubility Data Series 95-1mentioning

confidence: 63%

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 1. Introduction, Be and Mg

Visscher

Vanderdeelen

Königsberger

et al. 2012

Journal of Physical and Chemical Reference Data

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“…Figure 5 shows a comparison between the very detailed results of Patterson et al (3) and those calculated from eq. [18] using the expression log K, = log K,,, -log K,…”

Section: Standard State Propertiesmentioning

confidence: 96%

“…[4] for volumes, it is necessary to recognize that the heat capacity is a sum of contributions from the chemical species plus a contribution due to "relaxation" of the temperature dependent equilibrium represented by [3]. This effect is caused by a shift in the degree of dissociation due to the temperature increment imposed by the calorimeter in the course of measuring the heat capacity.…”

Section: Aqueous Sulfur Dioxidementioning

confidence: 99%

Thermodynamics of aqueous carbon dioxide and sulfur dioxide: heat capacities, volumes, and the temperature dependence of ionization

Barbero¹,

Hepler²,

McCurdy³

et al. 1983

Can. J. Chem.

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. Can. J. Chem. 61, 2509Chem. 61, (1983. A flow microcalorimeter and vibrating tubc densimeter were used at 25°C to obtain apparcnt molar heat capacitics and volumes of aqueous NaHCO1, KHCO,. NaHSO,, and KHSO, from 0. I to I .O mol kg-'. aqueous CO, from 0.01 to 0.10 mol kg-' and aqueous SO, from 0.045 to 2.0 mol kg-'. The contribution of "chemical relaxation" (changes in cquilibrium state and enthalpy due to change in temperature) to thc experimental heat capacitics of aqucous SO, required special attention, leading to the derivation of a new equation for calculating this cffcct. Standard statc valucs for thc heat capacities and volurnes of aqueous CO,, SOz, HCO,.., and H S O , were obtained from the apparent molar properties by extrapolation to infinite dilution. Combining these rcsults with othcr thcrmodynamic data from the literature gave estimates of log K,", the cquilibrium constant for the first neutralization of CO, and SO?, at high temperatures. The results for CO, reproducc very accuratc literature values to within 0.2 at 200°C. The expression for the reaction SO, t O H S HS0,-, log K l h = 22.771 t 2776.0/T -8.058 log T, is consistent with the sparse and limited experimental data.

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“…The length of time required to achieve thermal equilibrium and to conduct the titration causes the amino acids to decompose. Although flow cells exist for potentiometric titrimetry (Sweeton et al, 1973;Lvov et al, 1999), they are complex to operate and have been used in only a few studies (e.g., Patterson et al, 1982).…”

Section: Introductionmentioning

confidence: 99%

Ionization constants of aqueous amino acids at temperatures up to 250°C using hydrothermal pH indicators and UV-visible spectroscopy: Glycine, α-alanine, and proline

Clarke

Collins

Roberts

et al. 2005

Geochimica et Cosmochimica Acta

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Abstract-Ionization constants for several simple amino acids have been measured for the first time under hydrothermal conditions, using visible spectroscopy with a high-temperature, high-pressure flow cell and thermally stable colorimetric pH indicators. This method minimizes amino acid decomposition at high temperatures because the data can be collected rapidly with short equilibration times. The first ionization constant for proline and ␣-alanine, K a,COOH , and the first and second ionization constants for glycine, K a,COOH and K a,NH4ϩ , have been determined at temperatures as high as 250°C. Values for the standard partial molar heat capacity of ionization, ⌬ r C p o , COOH and ⌬ r C p o , NH4ϩ , have been determined from the temperature dependence of ln (K a,COOH ) and ln (K a,NH4ϩ ). The methodology has been validated by measuring the ionization constant of acetic acid up to 250°C, with results that agree with literature values obtained by potentiometric measurements to within the combined experimental uncertainty.We dedicate this paper to the memory of Dr. Donald Irish (1932-2002 of the University of Waterloofriend and former supervisor of two of the authors (R.J.B. and P.R.T.).

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Carbonate equilibria in hydrothermal systems: First ionization of carbonic acid in NaCl media to 300°C

Cited by 138 publications

References 33 publications

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 1. Introduction, Be and Mg

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 1. Introduction, Be and Mg

Thermodynamics of aqueous carbon dioxide and sulfur dioxide: heat capacities, volumes, and the temperature dependence of ionization

Ionization constants of aqueous amino acids at temperatures up to 250°C using hydrothermal pH indicators and UV-visible spectroscopy: Glycine, α-alanine, and proline

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