Solubility of pyromorphite Pb5(PO4)3Cl at 5–65°C and its experimentally determined thermodynamic parameters

Topolska, Justyna; Manecki, Maciej; Bajda, Tomasz; Borkiewicz, Olaf; Budzewski, Przemysław

doi:10.1016/j.jct.2016.03.031

Title: Solubility of pyromorphite Pb₅(PO₄)₃Cl at 5–65°C and its experimentally determined thermodynamic parameters

Abstract

Here, the solubility of synthetic pyromorphite Pb₅(PO₄)₃Cl was determined in a series of dissolution experiments conducted at 5–65 °C and at pH = 2.0. The equilibrium was established within 4 months. The dissolution of pyromorphite was congruent at all the temperatures, and the measured solubility product log K_sp,298 for the dissolution reaction: Pb₅(PO₄)₃Cl ⇌ 5Pb²⁺ + 3PO₄^3- + Cl^- was determined to be –79.6 ± 0.15. The equilibrium ion activity product of pyromorphite increased with temperature, indicating a positive enthalpy of the dissolution reaction in the temperature range from 5 to 65 °C. The temperature dependence of the log K_sp was nonlinear: log K_sp = A – B/T + D log(T), where A = 478.77 ± 136.62, B = 29,378 ± 6215, and D = –185.81 ± 46.77. This allowed for calculation of ΔG°_r = 454.0 ± 1.7 kJ·mol^–1, ΔH°_r = 101.8 ± 6.0 J·mol^–1·K^–1, ΔC°_p,r = –1545 ± 388.9 J·mol^–1·K^–1, and ΔS°_r = –1181 ± 382 J·mol^–1·K^–1 of the dissolution reaction. Using these values and the published standard state quantities for constituent ions, the values of ΔG°_f = –3764.3 ± 3.5 kJ·mol^–1, ΔH°_f = –4108.4 ± 7.9 J·mol^–1·K^–1, S°_f = 622 ± 382 J·mol^–1·K^–1, and C°_pf = 402 ±more »« less

Authors:

Topolska, Justyna ^[1]; Manecki, Maciej ^[1]; Bajda, Tomasz ^[1]; Borkiewicz, Olaf ^[2]; Budzewski, Przemysław ^[3]

AGH Univ. of Science and Technology, Krakow (Poland)
Argonne National Lab. (ANL), Argonne, IL (United States)
Predictive Solutions, Krakow (Poland)

Publication Date:: Sat Mar 19 00:00:00 EDT 2016

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:: Polish National Science Centre (NCN); AGH University of Science and Technology; USDOE

OSTI Identifier:: 1339458

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Thermodynamics

Additional Journal Information:: Journal Volume: 98; Journal Issue: C; Journal ID: ISSN 0021-9614

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; dissolution experiment; lead apatite; pyromorphite; solubility product; thermodynamics

Citation Formats


                    Topolska, Justyna, Manecki, Maciej, Bajda, Tomasz, Borkiewicz, Olaf, and Budzewski, Przemysław. Solubility of pyromorphite Pb5(PO4)3Cl at 5–65°C and its experimentally determined thermodynamic parameters.  United States: N. p., 2016. 
Web.  doi:10.1016/j.jct.2016.03.031.

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                    Topolska, Justyna, Manecki, Maciej, Bajda, Tomasz, Borkiewicz, Olaf, & Budzewski, Przemysław. Solubility of pyromorphite Pb5(PO4)3Cl at 5–65°C and its experimentally determined thermodynamic parameters.  United States.  https://doi.org/10.1016/j.jct.2016.03.031

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                    Topolska, Justyna, Manecki, Maciej, Bajda, Tomasz, Borkiewicz, Olaf, and Budzewski, Przemysław. Sat .  
"Solubility of pyromorphite Pb5(PO4)3Cl at 5–65°C and its experimentally determined thermodynamic parameters".  United States.  https://doi.org/10.1016/j.jct.2016.03.031.  https://www.osti.gov/servlets/purl/1339458.

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@article{osti_1339458,

  title        = {Solubility of pyromorphite Pb5(PO4)3Cl at 5–65°C and its experimentally determined thermodynamic parameters},

  author       = {Topolska, Justyna and Manecki, Maciej and Bajda, Tomasz and Borkiewicz, Olaf and Budzewski, Przemysław},

  abstractNote = {Here, the solubility of synthetic pyromorphite Pb5(PO4)3Cl was determined in a series of dissolution experiments conducted at 5–65 °C and at pH = 2.0. The equilibrium was established within 4 months. The dissolution of pyromorphite was congruent at all the temperatures, and the measured solubility product log Ksp,298 for the dissolution reaction: Pb5(PO4)3Cl ⇌ 5Pb2+ + 3PO43- + Cl- was determined to be –79.6 ± 0.15. The equilibrium ion activity product of pyromorphite increased with temperature, indicating a positive enthalpy of the dissolution reaction in the temperature range from 5 to 65 °C. The temperature dependence of the log Ksp was nonlinear: log Ksp = A – B/T + D log(T), where A = 478.77 ± 136.62, B = 29,378 ± 6215, and D = –185.81 ± 46.77. This allowed for calculation of ΔG°r = 454.0 ± 1.7 kJ·mol–1, ΔH°r = 101.8 ± 6.0 J·mol–1·K–1, ΔC°p,r = –1545 ± 388.9 J·mol–1·K–1, and ΔS°r = –1181 ± 382 J·mol–1·K–1 of the dissolution reaction. Using these values and the published standard state quantities for constituent ions, the values of ΔG°f = –3764.3 ± 3.5 kJ·mol–1, ΔH°f = –4108.4 ± 7.9 J·mol–1·K–1, S°f = 622 ± 382 J·mol–1·K–1, and C°pf = 402 ± 398 J·mol–1·K–1 were calculated for synthetic pyromorphite Pb5(PO4)3Cl.},

  doi          = {10.1016/j.jct.2016.03.031},

  journal      = {Journal of Chemical Thermodynamics},

  number       = C,

  volume       = 98,

  place        = {United States},

  year         = {Sat Mar 19 00:00:00 EDT 2016},

  month        = {Sat Mar 19 00:00:00 EDT 2016}

}

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Works referencing / citing this record:

Lead in Water and Soil: Speciation, Toxicity, and Treatment Technologies
book, January 2019

Manecki, Maciej
Encyclopedia of Water: Science, Technology, and Society
DOI: 10.1002/9781119300762.wsts0230

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Title: Solubility of pyromorphite Pb5(PO4)3Cl at 5–65°C and its experimentally determined thermodynamic parameters

Abstract

Citation Formats

Factors Influencing the Effectiveness and Stability of Aqueous Lead Immobilization by Hydroxyapatite journal, November 1996

Lead Immobilization from Aqueous Solutions and Contaminated Soils Using Phosphate Rocks journal, April 1995

Effects of Aqueous Al, Cd, Cu, Fe(II), Ni, and Zn on Pb Immobilization by Hydroxyapatite journal, July 1994

Effects of NO3-, Cl-, F-, SO42-, and CO32- on Pb2+ Immobilization by Hydroxyapatite journal, March 1994

In situ lead immobilization by apatite journal, September 1993

Comparative value of phosphate sources on the immobilization of lead, and leaching of lead and phosphorus in lead contaminated soils journal, January 2011

Uptake of aqueous Pb by Cl − , F − , and OH − apatites: Mineralogic evidence for nucleation mechanisms journal, July 2000

Pb remobilization by bacterially mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of phosphate-solubilizing Pseudomonas putida journal, July 2013

A comprehensive guide to experimental and predicted thermodynamic properties of phosphate apatite minerals in view of applicative purposes journal, February 2015

Lead orthophosphates—IV Formation and stability in the environment journal, June 1974

Equilibrium Solubility and Dissolution Rate of the Lead Phosphate Chloropyromorphite journal, December 2007

Solubility of pyromorphite Pb5(PO4)3Cl–mimetite Pb5(AsO4)3Cl solid solution series journal, April 2011

Calorimetric determination enthalpy of the formation of natural pyromorphite journal, January 2010

Thermochemistry and Relative Stability of Apatite Phosphates journal, January 2004

Synchrotron-based X-ray diffraction of the lead apatite series Pb 10 (PO 4 ) 6 Cl 2 –Pb 10 (AsO 4 ) 6 Cl 2 journal, February 2010

Effects of Aging and pH on Dissolution Kinetics and Stability of Chloropyromorphite journal, April 2002

Arsenite oxidation and arsenate determination by the molybdene blue method journal, November 2003

Solubility of mimetite Pb5(AsO4)3Cl at 5 - 55°C journal, January 2010

Siderophore Promoted Dissolution of Pyromorphite journal, January 2008

Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes journal, March 1997

The heat capacity and thermodynamic functions of pyromorphite over the temperature range 5–320 K journal, January 2011

Thermodynamics of aqueous phosphate solutions: Apparent molar heat capacities and volumes of the sodium and tetramethylammonium salts at 25�C journal, May 1995

Lead in Water and Soil: Speciation, Toxicity, and Treatment Technologies book, January 2019

Title: Solubility of pyromorphite Pb₅(PO₄)₃Cl at 5–65°C and its experimentally determined thermodynamic parameters

Factors Influencing the Effectiveness and Stability of Aqueous Lead Immobilization by Hydroxyapatite
journal, November 1996

Lead Immobilization from Aqueous Solutions and Contaminated Soils Using Phosphate Rocks
journal, April 1995

Effects of Aqueous Al, Cd, Cu, Fe(II), Ni, and Zn on Pb Immobilization by Hydroxyapatite
journal, July 1994

Effects of NO3-, Cl-, F-, SO42-, and CO32- on Pb2+ Immobilization by Hydroxyapatite
journal, March 1994

In situ lead immobilization by apatite
journal, September 1993

Comparative value of phosphate sources on the immobilization of lead, and leaching of lead and phosphorus in lead contaminated soils
journal, January 2011

Uptake of aqueous Pb by Cl ⁻ , F ⁻ , and OH ⁻ apatites: Mineralogic evidence for nucleation mechanisms
journal, July 2000

Pb remobilization by bacterially mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of phosphate-solubilizing Pseudomonas putida
journal, July 2013

A comprehensive guide to experimental and predicted thermodynamic properties of phosphate apatite minerals in view of applicative purposes
journal, February 2015

Lead orthophosphates—IV Formation and stability in the environment
journal, June 1974

Equilibrium Solubility and Dissolution Rate of the Lead Phosphate Chloropyromorphite
journal, December 2007

Solubility of pyromorphite Pb5(PO4)3Cl–mimetite Pb5(AsO4)3Cl solid solution series
journal, April 2011

Calorimetric determination enthalpy of the formation of natural pyromorphite
journal, January 2010

Thermochemistry and Relative Stability of Apatite Phosphates
journal, January 2004

Synchrotron-based X-ray diffraction of the lead apatite series Pb ₁₀ (PO ₄ ) ₆ Cl ₂ –Pb ₁₀ (AsO ₄ ) ₆ Cl ₂
journal, February 2010

Effects of Aging and pH on Dissolution Kinetics and Stability of Chloropyromorphite
journal, April 2002

Arsenite oxidation and arsenate determination by the molybdene blue method
journal, November 2003

Solubility of mimetite Pb5(AsO4)3Cl at 5 - 55°C
journal, January 2010

Siderophore Promoted Dissolution of Pyromorphite
journal, January 2008

Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes
journal, March 1997

The heat capacity and thermodynamic functions of pyromorphite over the temperature range 5–320 K
journal, January 2011

Thermodynamics of aqueous phosphate solutions: Apparent molar heat capacities and volumes of the sodium and tetramethylammonium salts at 25�C
journal, May 1995

Lead in Water and Soil: Speciation, Toxicity, and Treatment Technologies
book, January 2019