Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect
Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinka...
Ausführliche Beschreibung
Autor*in: |
Truesdale, Victor W. [verfasserIn] |
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Format: |
E-Artikel |
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Sprache: |
Englisch |
Erschienen: |
2012 |
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Übergeordnetes Werk: |
Enthalten in: Aquatic geochemistry - Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995, 18(2012), 3 vom: 10. Feb., Seite 217-241 |
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Übergeordnetes Werk: |
volume:18 ; year:2012 ; number:3 ; day:10 ; month:02 ; pages:217-241 |
Links: |
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DOI / URN: |
10.1007/s10498-012-9158-3 |
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Katalog-ID: |
SPR010512845 |
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520 | |a Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. | ||
650 | 4 | |a Gypsum dissolution |7 (dpeaa)DE-He213 | |
650 | 4 | |a Calcite dissolution |7 (dpeaa)DE-He213 | |
650 | 4 | |a Shrinking object model |7 (dpeaa)DE-He213 | |
650 | 4 | |a Dissolution kinetics |7 (dpeaa)DE-He213 | |
650 | 4 | |a Common-ion effect |7 (dpeaa)DE-He213 | |
650 | 4 | |a Batch dissolution |7 (dpeaa)DE-He213 | |
650 | 4 | |a Silicate-mineral dissolution |7 (dpeaa)DE-He213 | |
650 | 4 | |a Non-linear kinetics |7 (dpeaa)DE-He213 | |
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10.1007/s10498-012-9158-3 doi (DE-627)SPR010512845 (SPR)s10498-012-9158-3-e DE-627 ger DE-627 rakwb eng 550 ASE 38.32 bkl Truesdale, Victor W. verfasserin aut Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect 2012 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. Gypsum dissolution (dpeaa)DE-He213 Calcite dissolution (dpeaa)DE-He213 Shrinking object model (dpeaa)DE-He213 Dissolution kinetics (dpeaa)DE-He213 Common-ion effect (dpeaa)DE-He213 Batch dissolution (dpeaa)DE-He213 Silicate-mineral dissolution (dpeaa)DE-He213 Non-linear kinetics (dpeaa)DE-He213 Enthalten in Aquatic geochemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995 18(2012), 3 vom: 10. Feb., Seite 217-241 (DE-627)270935037 (DE-600)1478538-9 1573-1421 nnns volume:18 year:2012 number:3 day:10 month:02 pages:217-241 https://dx.doi.org/10.1007/s10498-012-9158-3 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-GGO SSG-OLC-ASE SSG-OPC-GGO SSG-OPC-ASE GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2360 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 38.32 ASE AR 18 2012 3 10 02 217-241 |
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10.1007/s10498-012-9158-3 doi (DE-627)SPR010512845 (SPR)s10498-012-9158-3-e DE-627 ger DE-627 rakwb eng 550 ASE 38.32 bkl Truesdale, Victor W. verfasserin aut Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect 2012 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. Gypsum dissolution (dpeaa)DE-He213 Calcite dissolution (dpeaa)DE-He213 Shrinking object model (dpeaa)DE-He213 Dissolution kinetics (dpeaa)DE-He213 Common-ion effect (dpeaa)DE-He213 Batch dissolution (dpeaa)DE-He213 Silicate-mineral dissolution (dpeaa)DE-He213 Non-linear kinetics (dpeaa)DE-He213 Enthalten in Aquatic geochemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995 18(2012), 3 vom: 10. Feb., Seite 217-241 (DE-627)270935037 (DE-600)1478538-9 1573-1421 nnns volume:18 year:2012 number:3 day:10 month:02 pages:217-241 https://dx.doi.org/10.1007/s10498-012-9158-3 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-GGO SSG-OLC-ASE SSG-OPC-GGO SSG-OPC-ASE GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2360 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 38.32 ASE AR 18 2012 3 10 02 217-241 |
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10.1007/s10498-012-9158-3 doi (DE-627)SPR010512845 (SPR)s10498-012-9158-3-e DE-627 ger DE-627 rakwb eng 550 ASE 38.32 bkl Truesdale, Victor W. verfasserin aut Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect 2012 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. Gypsum dissolution (dpeaa)DE-He213 Calcite dissolution (dpeaa)DE-He213 Shrinking object model (dpeaa)DE-He213 Dissolution kinetics (dpeaa)DE-He213 Common-ion effect (dpeaa)DE-He213 Batch dissolution (dpeaa)DE-He213 Silicate-mineral dissolution (dpeaa)DE-He213 Non-linear kinetics (dpeaa)DE-He213 Enthalten in Aquatic geochemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995 18(2012), 3 vom: 10. Feb., Seite 217-241 (DE-627)270935037 (DE-600)1478538-9 1573-1421 nnns volume:18 year:2012 number:3 day:10 month:02 pages:217-241 https://dx.doi.org/10.1007/s10498-012-9158-3 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-GGO SSG-OLC-ASE SSG-OPC-GGO SSG-OPC-ASE GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2360 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 38.32 ASE AR 18 2012 3 10 02 217-241 |
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10.1007/s10498-012-9158-3 doi (DE-627)SPR010512845 (SPR)s10498-012-9158-3-e DE-627 ger DE-627 rakwb eng 550 ASE 38.32 bkl Truesdale, Victor W. verfasserin aut Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect 2012 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. Gypsum dissolution (dpeaa)DE-He213 Calcite dissolution (dpeaa)DE-He213 Shrinking object model (dpeaa)DE-He213 Dissolution kinetics (dpeaa)DE-He213 Common-ion effect (dpeaa)DE-He213 Batch dissolution (dpeaa)DE-He213 Silicate-mineral dissolution (dpeaa)DE-He213 Non-linear kinetics (dpeaa)DE-He213 Enthalten in Aquatic geochemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995 18(2012), 3 vom: 10. Feb., Seite 217-241 (DE-627)270935037 (DE-600)1478538-9 1573-1421 nnns volume:18 year:2012 number:3 day:10 month:02 pages:217-241 https://dx.doi.org/10.1007/s10498-012-9158-3 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-GGO SSG-OLC-ASE SSG-OPC-GGO SSG-OPC-ASE GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2360 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 38.32 ASE AR 18 2012 3 10 02 217-241 |
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10.1007/s10498-012-9158-3 doi (DE-627)SPR010512845 (SPR)s10498-012-9158-3-e DE-627 ger DE-627 rakwb eng 550 ASE 38.32 bkl Truesdale, Victor W. verfasserin aut Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect 2012 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. Gypsum dissolution (dpeaa)DE-He213 Calcite dissolution (dpeaa)DE-He213 Shrinking object model (dpeaa)DE-He213 Dissolution kinetics (dpeaa)DE-He213 Common-ion effect (dpeaa)DE-He213 Batch dissolution (dpeaa)DE-He213 Silicate-mineral dissolution (dpeaa)DE-He213 Non-linear kinetics (dpeaa)DE-He213 Enthalten in Aquatic geochemistry Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995 18(2012), 3 vom: 10. Feb., Seite 217-241 (DE-627)270935037 (DE-600)1478538-9 1573-1421 nnns volume:18 year:2012 number:3 day:10 month:02 pages:217-241 https://dx.doi.org/10.1007/s10498-012-9158-3 lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER SSG-OLC-GGO SSG-OLC-ASE SSG-OPC-GGO SSG-OPC-ASE GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2360 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 38.32 ASE AR 18 2012 3 10 02 217-241 |
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Enthalten in Aquatic geochemistry 18(2012), 3 vom: 10. Feb., Seite 217-241 volume:18 year:2012 number:3 day:10 month:02 pages:217-241 |
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Gypsum dissolution Calcite dissolution Shrinking object model Dissolution kinetics Common-ion effect Batch dissolution Silicate-mineral dissolution Non-linear kinetics |
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<?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>01000caa a22002652 4500</leader><controlfield tag="001">SPR010512845</controlfield><controlfield tag="003">DE-627</controlfield><controlfield tag="005">20220110220920.0</controlfield><controlfield tag="007">cr uuu---uuuuu</controlfield><controlfield tag="008">201005s2012 xx |||||o 00| ||eng c</controlfield><datafield tag="024" ind1="7" ind2=" "><subfield code="a">10.1007/s10498-012-9158-3</subfield><subfield code="2">doi</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-627)SPR010512845</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(SPR)s10498-012-9158-3-e</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-627</subfield><subfield code="b">ger</subfield><subfield code="c">DE-627</subfield><subfield code="e">rakwb</subfield></datafield><datafield tag="041" ind1=" " ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="082" ind1="0" ind2="4"><subfield code="a">550</subfield><subfield code="q">ASE</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">38.32</subfield><subfield code="2">bkl</subfield></datafield><datafield tag="100" ind1="1" ind2=" "><subfield code="a">Truesdale, Victor W.</subfield><subfield code="e">verfasserin</subfield><subfield code="4">aut</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="c">2012</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="a">Text</subfield><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="a">Computermedien</subfield><subfield code="b">c</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="a">Online-Ressource</subfield><subfield code="b">cr</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="520" ind1=" " ind2=" "><subfield code="a">Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed.</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Gypsum dissolution</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Calcite dissolution</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Shrinking object model</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Dissolution kinetics</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Common-ion effect</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Batch dissolution</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Silicate-mineral dissolution</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="650" ind1=" " ind2="4"><subfield code="a">Non-linear kinetics</subfield><subfield code="7">(dpeaa)DE-He213</subfield></datafield><datafield tag="773" ind1="0" ind2="8"><subfield code="i">Enthalten in</subfield><subfield code="t">Aquatic geochemistry</subfield><subfield code="d">Dordrecht [u.a.] : Springer Science + Business Media B.V, 1995</subfield><subfield code="g">18(2012), 3 vom: 10. 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Truesdale, Victor W. |
spellingShingle |
Truesdale, Victor W. ddc 550 bkl 38.32 misc Gypsum dissolution misc Calcite dissolution misc Shrinking object model misc Dissolution kinetics misc Common-ion effect misc Batch dissolution misc Silicate-mineral dissolution misc Non-linear kinetics Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect |
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550 ASE 38.32 bkl Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect Gypsum dissolution (dpeaa)DE-He213 Calcite dissolution (dpeaa)DE-He213 Shrinking object model (dpeaa)DE-He213 Dissolution kinetics (dpeaa)DE-He213 Common-ion effect (dpeaa)DE-He213 Batch dissolution (dpeaa)DE-He213 Silicate-mineral dissolution (dpeaa)DE-He213 Non-linear kinetics (dpeaa)DE-He213 |
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ddc 550 bkl 38.32 misc Gypsum dissolution misc Calcite dissolution misc Shrinking object model misc Dissolution kinetics misc Common-ion effect misc Batch dissolution misc Silicate-mineral dissolution misc Non-linear kinetics |
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ddc 550 bkl 38.32 misc Gypsum dissolution misc Calcite dissolution misc Shrinking object model misc Dissolution kinetics misc Common-ion effect misc Batch dissolution misc Silicate-mineral dissolution misc Non-linear kinetics |
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Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect |
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Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect |
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author_browse |
Truesdale, Victor W. |
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550 ASE 38.32 bkl |
format_se |
Elektronische Aufsätze |
author-letter |
Truesdale, Victor W. |
doi_str_mv |
10.1007/s10498-012-9158-3 |
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550 |
title_sort |
unifying batch-dissolution kinetics for salts: probing the back reaction for gypsum and calcite by means of the common-ion effect |
title_auth |
Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect |
abstract |
Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. |
abstractGer |
Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. |
abstract_unstemmed |
Abstract Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, csat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by %$ {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) %$, where kb is a rate constant, and c can be expressed alternatively in terms of either [$ Ca^{2+} $], [$ SO_{4} $2−] and [$ ε_{±} $], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [$ SO_{4} $2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon csat, kb and kf, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, csat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sjöberg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed. |
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container_issue |
3 |
title_short |
Unifying Batch-Dissolution Kinetics for Salts: Probing the Back Reaction for Gypsum and Calcite by Means of the Common-Ion Effect |
url |
https://dx.doi.org/10.1007/s10498-012-9158-3 |
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score |
7.400259 |