Sodium Phosphate Hideout Mechanisms

Data and Models for the Solubility and Redox Behavior of Iron(II) and Iron(III) Sodium-Phosphate Hideout Reaction Products
TR-112137

Final Report, May 1999

Effective December 6, 2006, this report has been made publicly available in accordance with Section 734.3(b)(3) and published in accordance with Section 734.7 of the U.S. Export Administration Regulations. As a result of this publication, this report is subject to only copyright protection and does not require any license agreement from EPRI. This notice supersedes the export control restrictions and any proprietary licensed material notices embedded in the document prior to publication.

EPRI Project Manager R. B. Dooley

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CITATIONS
This report was prepared by Department of Chemistry Memorial University of Newfoundland St. John’s, NF, Canada A1B 3X7 Principal Investigators P. Tremaine D. Schvedov L. Trevani C. Xiao This report describes research sponsored by EPRI. The report is a corporate document that should be cited in the literature in the following manner: Sodium Phosphate Hideout Mechanisms: Data and Models for the Solubility and Redox Behavior of Iron(II) and Iron(III) Sodium-Phosphate Hideout Reaction Products, EPRI, Palo Alto, CA: 1999. TR-112137.

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which is the form of protective oxide in an operating boiler. Objectives • To conduct detailed laboratory studies to measure the solubility and calorimetric data of maricite and (Na4Fe(OH)(PO4)2 (SIHP). Results The following are the key results from the project: v . there was no reliable corrosion data to confirm the mechanism. Volumes 1 and 2)) and related the corrosion product. they related the laboratory data to the solubility of magnetite. Finally. which are two possible corrosion products. Background The Phosphate Treatment Guidelines (TR-103665) were issued in 1994 to counteract two major problems that were occurring in the industry: (1) phosphate hideout and return and (2) acid phosphate corrosion (APC). They then developed a solubility and thermodynamic model for both compounds.REPORT SUMMARY The quality of boiler water and steam is central to ensuring power plant component availability and reliability. However. Approach The project team designed and built apparatus to measure the solubility of maricite and SIHP and used a differential scanning calorimeter equipped with thermal analysis software to measure the heat capacities. Over 70% of drum units operate with phosphate treatment. This study confirms the philosophy behind EPRI’s Phosphate Treatment Guidelines. The team synthesized both maricite and SIHP and measured the kinetics of formation as a function of various Na:PO4 ratio solutions. • To develop a model that identifies the plant conditions responsible for serious corrosion reactions. maricite. to the addition of acidic phosphate chemicals during hideout periods. EPRI had demonstrated an understanding of the APC mechanism (TR-102433.

• At higher Na:PO4 ratios.• Thermodynamic constants were derived for phosphate hideout and corrosion reactions resulting in maricite and SIHP from 200-325°C.2 can result in the formation of maricite and cause serious damage fully supports the mechanism of severe corrosion of carbon steel boiler tubes operated under congruent phosphate treatment (CPT).8). Certainly. the philosophy of not adding any solutions of mono.2 can cause extensive attack of magnetite to form maricite and hematite.6) to equilibrium phosphate treatment (EPT) and phosphate treatment (PT) (with Na:PO4 ratios greater than 2. EPRI Perspective The finding that boiler water at Na:PO4 ratios below 2. • The constants were incorporated into EPRI’s MULTEQ code to assess the nature of the corrosion reactions with magnetite that occur at different Na:PO 4 ratios.or di-sodium phosphate during hideout— but only allowing additions of trisodium phosphate—appears key to avoiding corrosion problems. the formation of SIHP from the reactions between magnetite and sodium phosphate may be the major reaction controlling boiler water chemistry under hideout conditions. there has been a marked reduction of operating and corrosion problems on units using EPT and PT since the introduction of the EPRI Guidelines in 1994. TR-112137 Keywords Power plant availability Water chemistry Boilers Phosphates Corrosion Boiler tube failures vi . • The data indicates that corrosion in boiler water at Na:PO4 ratios below 2. Thus. This work also supports change of the EPRI guidelines from CPT (with Na:PO4 ratios of less than 2.

structure. Maricite has been identified in power station deposits. Quinlan. and an iron(III) phase. and some solubility data for SIHP. The results predict major damage to magnetite films at low sodium phosphate ratios. maricite (NaFeIIPO4). Recent work by Ziemniak and Opalka (1992. The iron (III) phase is unstable under ambient conditions in the presence of water. and redissolves in boiler water on cooling. 1993) and by the current investigators (Tremaine et al..EPRI Licensed Material ABSTRACT The objective of this project was to develop a database and chemical equilibrium models capable of predicting the onset of detrimental sodium phosphate hideout reactions in fossil power station boilers. The database on SIHP was not complete under the full range of boiler conditions and there are no thermodynamic constants whatsoever for maricite in the literature. sodium iron hydroxy phosphate. 1998.. vii . and to identify conditions leading to corrosive attack on magnetite films. Until recently its properties were largely unknown. The objective of this research program was to complete the database for sodium phosphate reactions with magnetite: (i) by obtaining solubility data for maricite under controlled redox conditions and fitting a speciation model to the new data by determining further solubility data for SIHP and refitting the data determined by Quinlan (1996) to the new speciation model (ii) (iii) by obtaining calorimetric data needed to extrapolate solubility results for both maricite and SIHP to higher and lower temperatures The results have been incorporated into a chemical equilibrium model consistent with the EPRI code MULTEQ and the equations needed to construct solubility and Eh-pH diagrams for the hideout reactions have been derived. Sodium-phosphate hideout in high pressure boilers is now known to be caused by reversible reactions between aqueous phosphate and magnetite that result in the formation of sodium iron phosphate compounds. 1996) has identified the formula. (Na4Fe(OH)(PO4)2·1/3NaOH) abbreviated as “SIHP”. Bridson et al. 1996. The equilibrium model has been used to assess the conditions under which iron phosphate hideout reactions take place.

viii .2 causes extensive attack on magnetite to form hematite and maricite. the formation of SIHP and hydrogen from the oxidation of magnetite by sodium phosphate may be the major reaction controlling water chemistry under hideout conditions. to determine thermodynamic constants for the phosphate-hideout reaction products SIHP and maricite. The results of this work. and by calorimetry. (v) At higher Na/PO4 ratios. and the earlier thesis work of Quinlan.EPRI Licensed Material These predictions are consistent with field experience. The reaction yields local conditions which are reducing and alkaline. may be summarized as follows: (i) Extensive laboratory measurements have been made by pressure vessel techniques from 200 to 325°C. and to extend the chemical equilibrium model to higher sodium phosphate ratios and higher temperatures consistent with the operating conditions in high pressure boilers. not the much lower molalities of residual dissolved oxygen or redox buffers in the boiler water (ii) (iii) The thermodynamic constants for SIHP and maricite have been incorporated into the EPRI chemical equilibrium program MULTEQ and used to assess the nature of the hideout reactions with magnetite that occur at different sodium phosphate ratios. Recommendations have been made for future work to examine the impact of detrimental hideout reactions on corrosion. (iv) The results show for the first time that hideout from boiler water at sodiumphosphate ratios below about 2. These may yield beneficial effects which inhibit further corrosion and thus compensate for modest reductions in pressure tube thickness arising from the hideout reaction itself. where major corrosion reactions appear to take place. This finding supports the mechanism for the severe corrosion of carbon steel boiler tubes in some stations operated under congruent phosphate chemistry control first discussed by Dooley and Paterson (1994). The redox chemistry of magnetite during hideout is controlled by the molalities of the dissolved sodium phosphate species.

Barry Dooley. Maggie Piranian and Ms. for professional and prompt assistance in identifying the causes of the accident and putting revised procedures in place. and the safety committees in the Chemistry and Earth Science Departments. We thank Mr. a serious accident associated with the hydrogen gas handling occurred during the course of the project.EPRI Licensed Material ACKNOWLEDGMENTS The experimental foundation for this project is based on the work on SIHP reported in Sean Quinlan’s MSc thesis. We stress the need to use all of the precautions noted in Section 2 with scrupulous attention to detail. for much constructive input and advice during the early stages of the work. and to Carl Mulcahy and George Pardy from the electronics shops for their very able and timely assistance. Peter Haring of the Newfoundland Dept. Our EPRI project manager. Steve Ziemniak and Mr. Jan Stodola are also gratefully acknowledged. Frank Smith. Ms. provided backgound information. Although many of the safety precautions outlined in Section 2 were in place. Carolyn Emerson of Memorial University provided training and much assistance with the powder X-ray diffraction studies and electron microscopy. We are especially grateful to Randy Thorne. Quinlan for permission to use his results in our data analysis. Chris Finch and Mr. and express our gratitude to the Memorial University safety officers. The competent and professional assistance of the Memorial University Technical Services were essential to this project. advice and encouragement on many aspects related to the use of phosphate in thermal power stations. and for providing samples of SIHP and maricite. The ICP-ES analyses were carried out by Mr. and especially to Dr. ix . of Mines and Energy. Helpful discussions with Dr. from the machine shop. and Boyd Parsons. Dr. Paul Martin.

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............ 2-5 2........................................ 1-12 1.......................1..............................3......................................... 1-17 1...1 Chemical and Materials.............. 1-4 1...................................................................EPRI Licensed Material CONTENTS 1 INTRODUCTION ..................1 Stirred Reaction Vessel ...................................... 2-1 2................... 1-15 1....................................................4.............................4.....................2 The Chemistry of Aqueous Sodium Phosphate at Elevated Temperatures ................................................................................1 Hideout Reaction Products: Sodium Iron(III) Hydroxy Phosphate (“SIHP”) and Maricite.........................................................................1 Phosphate Hideout in Fossil Boilers ................................................................................... 1-12 1............................. 2-1 2............................................................3 Solubility Experiments on SIHP ..... 1-17 1..............3 Analytical Methods ..................... 1-16 1................. 2-3 2.........4 Solubility and Kinetic Measurements in the Stirred Reaction Vessel ...............4......................2 Calorimetric Data for Maricite and Sodium Iron (III) Hydroxy Phosphate ..........................3 Thermodynamic Data From Solubility Studies ....................................................................................................................1 Powder X-Ray Diffraction .1 Project Objectives and Workplan................5 Thermodynamic Modelling:.............................................................................................................1......................................... 2-1 2..........................................................3... 2-5 2..4.......2 Calorimetric Measurements.....4...................... 1-13 1................. 1-1 1..............3 Sodium Phosphate Reactions with Magnetite ..2......2 ICP Emission Spectroscopy . 2-5 2........................................3..............2 Flow and Batch Experiments Under Steam Generator Conditions...................................2 Modifications for Use With Hydrogen..................................1 Experimental Design ....................................................................................... 2-1 2.........2 Solubility Apparatus ...............4................ 1-16 1................... 2-6 2...2......... 2-3 2............................ 2-4 2........................ 1-1 1.......... 1-18 1.....3......................................................................................................................4 Solubility Experiments on Maricite ........ 2-6 xi ......................................................................................................1 Solubility Studies .......3............................................ 1-18 2 EXPERIMENTAL .................................4 The EPRI Project .........................

..... 3-9 3....................................................................... 3-6 3..............................................................................3 Equilibrium Constants for SIHP ....................... 2-10 2..............................................................................................................1 Dissolution of Maricite in HClO4(aq)...................5 Model II .................... 2-9 2........ 4-7 4.........5 Discussion.3 Heat of Solution Results...... 4-7 4................ 4-14 5 SOLUBILITY AND THERMODYNAMIC MODEL FOR MARICITE........................................1 Experimental Results for SIHP ...................1 Kinetics................................2 Kinetics of the Sodium Phosphate-Magnetite Reaction .......1 Standard Thermodynamic Properties ........4.1 Experimental Results for Maricite................................. 4-13 4...................4...................................................................2 Solubility ............4...... 5-3 xii ..........................4.............................4 Enthalpy Calculations....... cr) AND SODIUM IRON(III) HYDROXY PHOSPHATE (Na3Fe(PO4)2·(Na4/3H2/3O)..................................................5 Discussion...................................................................................... 2-9 2. 3-3 3.... 4-3 4........................................................4 A Thermodynamic Model ...............................................................4.................... .. cr) ............................ 4-1 4.................4................2 Kinetics of the Sodium Phosphate-Hematite Reaction ......1 Heat Capacity Measurements ..................5 Calorimetric Measurements . 4-9 4.....................EPRI Licensed Material 2...................................4...........................................................4........................ 2-9 2.....................................................................1 Introduction ................................................................................ 3-6 3..................4................................................................... 4-3 4.................. 3-3 3.............................................................................. 3-1 3................................................................................................................3 Solubility of SIHP in Equilibrium with Hematite................................................................3.................................3..............................................4............................................................................. 5-1 5... 4-1 4.........................2 Activity Coefficient Model..4................................................................................................3 Measurements on Maricite.................... 2-10 2......................................................................................3 Heats of Mixing................ 3-12 4 SOLUBILITY AND THERMODYNAMIC MODEL FOR SIHP..........................................................4 Model I ......................................................................................... 4-12 4.5............4......... 3-10 3.......... 2-10 2.............................................................2 Heat Capacity Results.5.................... 5-1 5......2 Dissolution of SIHP in HClO4(aq) .......... 2-11 3 ENTHALPIES OF FORMATION AND HEAT CAPACITY FUNCTIONS FOR MARICITE (NaFePO4................................................................................................................................. 3-1 3.............2 Heats of Solution ................. 4-8 4...............................................................................2 Measurements on SIHP ....................

................................6.6 Discussion ................. A-1 A...................................4...................................................3 Solubility of Gases in Aqueous Electrolyte Solutions At Elevated Temperatures ...................................................................... 5-16 Magnetite Oxidation to SIHP .. 6-7 6........ Solids and Gases ............................................................................................................................... 5-12 5.............................................EPRI Licensed Material 5............................................................................. 5-5 5....... 5-9 5................ A-1 A..............................................1 Standard State Properties of Aqueous Species.................4......................................................................5............................................................. 5-12 5........ 6-12 7 REFERENCES ..................... A-1 A.....................................................4 A Thermodynamic Model .................................................................... 6-1 6.....3 Hideout Reactions at Moderate to High Na/PO4 Ratios ..........................5............... A-3 A........................................................................2 Models I and II .................2 A Mechanism for Severe Corrosion Damage at Low Na/PO4 Ratios .............................1 Solids and Gases..2 Activity Coefficients in High Temperature Water ......................................2 p(H2) .................4 Conclusions and Recommendations................... 5-16 Magnetite Oxidation to Hematite .. 5-6 5................................2 Aqueous Species.............................1................................................................... 7-1 A THE THERMODYNAMICS OF AQUEOUS SPECIES........................1 The Stability of Magnetite Films ......................6...................................5 Comparison with Experimental Solubilities ..1 Magnetite Redox Equilibria with Aqueous Sodium Phosphate in High Temperature Water .......................................... 5-12 5..... 6-1 6............................................................................................................................. SOLIDS AND GASES .................................................................................................1 Equilibrium Constants for Maricite........ 5-17 5....... 5-16 5................................................................T Diagram .................................................................................... 5-17 Hematite Reduction to Maricite .............. 5-17 6 MAGNETITE STABILITY UNDER HIDEOUT CONDITIONS AND IMPLICATIONS FOR POWER STATION CHEMISTRY CONTROL STRATEGIES ................................................ 5-16 SIHP Reduction to Maricite . Solids and Gases ... 5-17 SIHP Formation from Hematite ................2 Maricite + Magnetite + SIHP ...1.................................1 Maricite + Magnetite + Hydrogen .................... 5-16 Magnetite Reduction to Maricite.................................... 5-6 5........................................3 Solubility of Maricite in Equilibrium with Magnetite and Hydrogen .......................................................................................... 6-8 6........................................ A-7 xiii ............ A-5 A..........A-1 The Thermodynamics of Aqueous Species.........

..............................................................B-1 xiv .............................................................EPRI Licensed Material B THERMODYNAMIC CONSTANTS FOR THE SODIUM/PHOSPHATE/IRON/WATER SYSTEM .......

..........5 (Quinlan 1996) : (solid symbols)................................... .....-.............. 1-9 Figure 1-3 Liquid-liquid and solid-liquid phase boundaries for aqueous solutions of sodium phosphate salts at Na/PO4 mole ratios from 1.................. In Hastelloy vessels. pH 10 corresponds to an alkalinity m(OH ) = 10 -1 -4 -1 mol....................-................... Model I.......... ...... 2-4 Figure 2-2 Pressure calibration curves showing hysteresis in the pressure transducer response due to friction in the piston-cylinder isolator.......................2 (this work)...... ........................... b: (Na/PO4)initial = 3.................................................... 1982)................................................................................................................................1 < Na/PO4 < 2...........EPRI Licensed Material LIST OF FIGURES Figure 1-1 The distribution of phosphate species at 25 and 300°C at I=0....... Model II......................... configured for studies with hydrogen ....................-................ ______.... 2-7 Figure 2-3 Solubility data for SIHP in equilibrium with hematite. 2-8 Figure 3-1 Crystal structure of SIHP ....00 to 3...27 as a function of temperature: -............................... calculated from -2 the data in Appendix A............ _____....................... ..................................... 4-6 Figure 4-3 Comparison of experimental and predicted equilibrium quotients for the second ionization of phosphoric acid...........-..........0 (Quinlan.................... 4-9 Figure 4-4 Experimantal data for the Gibbs energy of formation of SIHP (∆aG°) for ratios from this work and Quinlan (1996)......................................... 3-2 Figure 4-1 The relative concentration of phosphoric acid species in the solubility data for SIHP in equilibrium with hematite for (Na/PO4)initial = 2... plotted as a function of temperature: -............-...... 1996)..kg compared to 10 mol kg at 25°C......... 4-11 Figure 4-5 Experimental data for the Gibbs energy formation of SIHP (∆aG) for solids with stoichiometry 2... the steps must be small enough to avoid crossing the reaction threshold with nickel (Quinlan...................... 1-7 Figure 1-2 The solubility of trisodium phosphate in high temperature water as a function of temperature................-........................... 1996)................................... 1993)........................... 4-5 Figure 4-2 The relative concentration of phosphoric acids species in the solubility data for SIHP in equilibrium with hematite for a: (Na/PO4)initial = 2....... obtained by stepping up the temperature in a stirred batch reactor..... At 360°C the reaction to form SIHP oxidized magnetite to produce H2 at ratios Na/PO4 > 2........................00 at temperatures from 200 to 400°C (Marshall........... 1-10 Figure 1-4 Solubility of trisodium phosphate in aqueous sodium hydroxide (Boroyava and Ravich..... 1968) ...............................7...............-.............................. 1-14 Figure 2-1 Schematic diagram of the Parr 450 mL stirred reactor.......................................... model I............................................................. MULTEQ: (open symbols) from data in Table 4-4........ At 300°C... model II.............................................................. 1-11 Figure 1-5 Sodium phosphate hideout reactions with magnetite at 320 and 360°C from flow experiments (Tremaine et al............ 4-13 xv .......

......................................................aq)=0. 4-16 Figure 4-8 Hydroxide molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.T(maricite.................. 6-3 Figure 6-4 The sodium phosphate ratio in the solid hideout product from the calculation plotted in Figure 6-1..........2: solid symbols.. plotted as hydrogen molality m(H2).... ........................................2 ............. 4-15 Figure 4-7 Phosphate molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.................mcalc)/mexp.................. ....... 6-5 Figure 6-6 The redox potential corresponding to the calculation from Figure 6-1............... calculated from Model II.....8(H3O)0........................................................... 6-2 Figure 6-2 The percentage of Fe3O4 consumed as iron-containing reaction products from the calculation plotted in Figure 6-1....1 mol....... experimental.... “NaP28S” is the sodium phosphate phase Na2................ ................................. .............................................................................s) fixed......2: solid symbols............................. ∆fH°298(maricite.................................. 5-13 Figure 5-5 An approximate stability diagram for the iron/sodium/phosphate/water + -1 system.................... calculated from Model II..................................... experimental....... experimental.........08 mol............................. calculated with m(Na ............... ........ open symbols....................... open symbols............................................. 5-20 Figure 6-1 Calculated inventories of hideout reaction products when 0................................................2PO4.....T(maricite.......EPRI Licensed Material Figure 4-6 Sodium molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2........................... 4-18 Figure 4-10 Hydroxide molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2... ............................................ 6-4 Figure 6-5 Aqueous (Na/PO4) ratio and equilibrium pH from the calculation plotted in Figure 6-1.............................. 5-10 Figure 5-3 (a) sodium....... 5-11 Figure 5-4 Relative error of solubilities maricite-magnetite-hydrogen system calculated from Model II: 100 (mexp ...... 4-17 Figure 4-9 (a) sodium and (b) phosphate molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2..................aq) = 0. experimental........................... calculated from Model II........... 6-3 Figure 6-3 The inventories of aqueous phosphate consumed as reaction products in the calculation plotted in Figure 6-1............................. open symbols..... Na/PO4 = 2........... open symbols......kg phosphate solution at various (Na/PO4)initial ratios (from model II).....5 (Quinlan 1996): solid symbols..............1 mol.....0 and (b) Na/PO4 = 2.. calculated with m(Na .................................. 4-19 Figure 5-1 The kinetics of maricite formation at 237°C as evidenced by the decrease in sodium and total phosphate molalities to their equilibrium values after approximately 100 hours. calculated from Model II..... experimental......................s) and C°p.............5.. 5-18 Figure 5-6 An approximate stability diagram for the iron/sodium/phosphate/water + -1 system...................................................kg at low Na/PO4 ratios: (a) Na/PO4 = 2.......... experimental.......................... ..... 5-5 Figure 5-2 Experimental data for the Gibbs energy of formation of maricite (∆aG°) (a) Model I.............................................................. (b) Model II...2: solid symbols.5 (Quinlan 1996): solid symbols................... (b) phosphate and (c) hydroxide molalities of solutions in equilibrium with maricite and magnetite: solid symbols................................... open symbols......................................... calculated from Model II..kg Fe3O4 -1 reacts with 0....... ∆fH°298(maricite..........................s) fixed......25 mol...... open symbols.... ............................... ............... ..... calculated from Model II......................................................................................kg ............................ .... 6-6 -1 xvi ................................s) varied and C°p..............

... (b) Na/PO4 = 2...EPRI Licensed Material Figure 6-7 A schematic diagram of the reaction mechanism of Fe3O4 at 275°C corresponding to the calculation plotted in Figure 6-1........ and (c) Na/PO4 = 3.......0.....................aq) = 0. showing the hideout reaction paths during heating: (a) Na/PO4 = 2..5...... 6-10 Figure 6-8 Approximate stability diagram for the iron/sodium/phosphate/water system.. 6-11 xvii .....................2.................. + -1 calculated with m(Na .1 mol/kg .

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...................... activity of 2+ water and ionic strength for Reaction 4-4................................. 5-4 ← 2+ 0 -1 -1 -1 a xix ........ 1-5 Table 1-4 HKF equation of state coefficients for aqueous species ............................. 1-3 Table 1-2 Standard state properties* at 25°C and 1bar....................aq).................. ..................... 3-11 Table 4-1 Summary of the initial experimental conditions to determine the solubility of SIHP in this work.................. 4-2 Table 4-4 Equilibrium values for m(HPO4 . 3-5 Table 3-5 Parameters for heat of solution calculations............................... 3-8 Table 3-7 Standard partial molar enthalpies of formation at 25°C and 1 bar and MaierKelley coefficients for heat capacities of SIHP and maricite.................................................................... (Na4/3H2/3O) (s) + 5 H2O........ 5-2 Table 5-3 Kinetics of maricite formation at 237°C according to reaction 4-1: Fe3O4(s) + 3 2+ Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH + H2O.9461 kg · mol HClO4(aq) solutions........................9461 mol·kg-1) + H3PO4(aq.............9461 kg · mol HClO4(aq) solutions............. m(OH ............................ 4-13 Table 5-1 Summary of the initial experimental conditions used to determine the solubility of maricite.............................. 3-5 Table 3-4 Heats of mixing for {HClO4(aq.15 K.............. ............................................. 3 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2.............. 0.............................. 3-5 Table 3-3 Dissolution of SIHP in 0........... (Na4/3H2/3O) (s) + 5 H2O ................. 4-1 Table 4-2 Summary of the Quinlan’s (1996) initial experimental conditions to determine the solubility of SIHP............................................ 3-8 Table 3-6 Standard partial molar enthalpies of formation and ionization of H3PO4 (aq) at T=298....aq) and m(Na ....................... 1-5 Table 1-3 Maier-Kelley coefficients for heat capacities of solids and gases...... 5-2 Table 5-2 Thermodynamic functions of hydrogen in the vapour and aqueous phases................................................................ 1-6 Table 3-1 Experimental values for the molar heat capacities of SIHP and maricite................................. 4-10 ← Table 4-6 Standard state properties of SIHP at 25°C and 1bar.. ................................. (Na4/3H2/3O) (s) + 5 H2O ................................ 4-2 Table 4-3 Summary of the experimental solubility data of SIHP obtained in this work 2+ according to: 3 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 ← Na3Fe(PO4)2.........* (See Appendix A..................................... 3-4 Table 3-2 Dissolution of maricite in 0..... 4-4 ← Table 4-5 Thermodynamics of SIHP formation according to Reaction 4-4: 3 Fe2O3(s) + 2+ 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2............................ 1...................................).........EPRI Licensed Material LIST OF TABLES Table 1-1 Summary of thermodynamic equations used in this work...................* .................................* .....aq). ..................181 mol·kg )} ....................................................................

. ...................................................... 5-15 2+ xx ....... 5-14 Table 5-9 Comparison between the experimental solubility of maricite and the MULTEQ simulation results..................................................................... 5-6 Table 5-5 Equilibrium values for m(HPO4 ............................EPRI Licensed Material Table 5-4 Summary of the experimental runs on the solubility of maricite according to: 2+ Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH (aq) + ← H2O(l) .................................... ..................... activity of water and ionic strength for the 2+ maricite formation reaction: Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 ← NaFePO4(s) + 3 OH (aq) + H2O(l).aq)................... 5-12 Table 5-8 Solubility corresponding to 3 ........ m(OH ..... 5-8 Table 5-6 Thermodynamics data of maricite formation according to reaction 5-1: 2+ Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH + H2O. 5-9 ← Table 5-7 Standard state properties of maricite at 25°C and 1bar.....................aq).............phase mixtures of reaction products................. partial pressure and activity of hydrogen....................................................................................................aq) and m(Na ..

EPRI Licensed Material 1 INTRODUCTION 1. 1992. 1975. Systematic studies of the pure sodium phosphate water phase diagram have demonstrated that hideout can be caused by the precipitation of sodium phosphate phases at local hot spots and under deposits (Ravich and Scherbakova. Dooley and McNaughton. Phosphate “hideout” is characterized by the retention of phosphate in the boiler during conditions of increasing load or pressure. The hideout reaction products that form under high pressure boiler conditions have now been identified (Tremaine et al. 1992. even during evaporation to dryness at temperatures in excess of 300°C (Panson et al..1 Phosphate Hideout in Fossil Boilers Sodium-phosphate based boiler water treatments are used by the electric power industry to buffer pH and to control scale in the drum boilers of fossil power stations. 1996) .. Connor and Panson. In the late 1980s..... 1993. 1994) have shown that some of this damage can be attributed to ironphosphate reactions associated with hideout under congruent phosphate conditions. 1993. Panson et al. Broadbent et al. 1983. This data base does not yet exist. 1984). The nature of the attack suggested that other potentially damaging hideout mechanisms must also exist. The introduction of “congruent” phosphate control in the 1980's was intended to maintain a position in the phase diagram that would avoid pH excursions. Economy et al. may arise from incongruent precipitation reactions at local sites when hideout takes place. 1978. and its subsequent release when the load or pressure is reduced. Layton. 1992. 1975. 1955. 1994. Dooley et al. Ziemniak and Opalka.1975. Very high concentrations of phosphate. 1977). Taylor et al. 1994.. and a mechanism for the initiation step has been proposed (Dooley and Paterson. 1994. and field studies (Dooley and Paterson. 1987). Research in several laboratories (Tremaine et al. Ziemniak and Opalka. The hideout in high pressure boilers associated with iron-phosphate interactions is now known to be caused by reversible reactions between aqueous phosphate and magnetite 1-1 .. 1996). 1979. 1993). accompanied by extreme pH excursions. Aschoff et al.. Quantitative data for the solubility and redox equilibria of these previously unknown compounds are badly needed to predict the onset of hideout and to identify the conditions for corrosive attack under high pressure boiler conditions. Broadbent et al. severe corrosion problems that arose in some units were associated with the practical application of congruent phosphate control (Dooley and Paterson.

The work summarized above has identified the major sodium iron phosphate phases and many aspects of the role of SIHP in phosphate hideout under high pressure boiler conditions. Until recently its properties were largely unknown.EPRI Licensed Material Introduction that result in the formation of sodium iron phosphate compounds.. 1996. Tremaine et al. Quinlan. and some solubility data for SIHP. (1996) have shown that. Bridson et al. and redissolves in water on cooling. further experiments were needed to complete the thermodynamic model for this system. Recent work by Ziemniak and Opalka (1992. 1998. during phosphate hideout. where major corrosion reactions appear to take place. and an iron(III) phase. 1996) has identified the formula. 1994). rather than by the much smaller concentrations of dissolved oxygen and residual reducing agents. The objective of this research program was to complete the database for sodium phosphate reactions with magnetite: (i) by obtaining solubility data for maricite under controlled redox conditions and fitting a speciation model to the new data by determining further solubility data for SIHP and refitting the data determined by Quinlan (1996) to the new speciation model by obtaining calorimetric data needed to extrapolate solubility results for both maricite and SIHP to higher and lower temperatures (ii) (iii) The results have been incorporated into an equilibrium model consistent with the EPRI code MULTEQ and the equation needed to construct solubility and Eh-pH diagrams for the hideout reactions have been derived. The crystal structure of SIHP and the predominant role of aqueous sodium phosphate in controlling the redox chemistry of its formation from magnetite are particularly significant. There were no themodynamic constants whatsoever for maricite under high pressure boiler conditions. 1993) and by the current investigators (Tremaine et al. The remainder of this introductory section presents a review of the current state-of-theart knowledge for phosphate speciation and hideout equilibria in water at high temperatures and pressures. Maricite has been identified in power station deposits (Dooley and Paterson. The equilibrium model has been used to identify the condition consistent with field experience. structure. the local redox chemistry is largely controlled by the sodium and phosphate concentrations in solution. (Na4Fe(OH)(PO4)2·1/3NaOH) which is abbreviated to “SIHP”. The iron (III) phase is unstable under ambient conditions in the presence of water. The final part of the section is a detailed summary of the 1-2 . The reaction to form either phase from magnetite depends on the local redox potential. sodium iron hydroxy phosphate. While significant advances have been made towards the development of a model for the hideout and release of SIHP. maricite (NaFeIIPO4)..

Table 1-1 Summary of thermodynamic equations used in this work.S T r .Θ )   (A-6) o Cp = c1 + c2 (T .Θ )3  ψ + pr  2T 1  a4  a2 +  a3 + ψ + p  .p° at elevated temperature and pressure: o ∆ a GT.T r )+ Tr ∫ T C o dT .∑ ∆ f GT (reactants) (A-10) (A-11) Apparent Gibbs energies of formation ∆aGT.p° : ∆ r GT = ∑ ∆ a GT (products) .Θ )2 (A-17) o V = a1 + (A-18) _____________________________________________________________________________ * Equation numbers are from Appendix A. The thermodynamic equations are summarized in Table 1-1.∑ ∆ a GT (reactants) o o o o o = ∑ ∆ f GT (products) . p r .T p Tr ∫ T C o /T dT + p pr ∫ p V o dp (A-9) Standard molar heat capacities of solids and gases: C o = a + bT + cT -2 p Standard partial molar heat capacities and volumes of aqueous species:   a (p .RT ln K Equilibrium constants K and Gibbs energies of reaction ∆rGT.ω Q ψ + p (T .EPRI Licensed Material project objectives and workplan.* (See Appendix A.) _____________________________________________________________________________ ∆ r Go = . The thermodynamic framework and a description of the equations used in this work are outlined in Appendix A.p ) + a ln ψ + p  + ωTX 4 r  3  (T . p r (T . p = o o ∆ f GT r . 1-3 .

solids and dissolved gases consistent with the equations in Appendix A are listed in Tables 1-2 to 1-4. hydrogen phosphate. The major phosphate species in high-temperature water are the anions of orthophosphoric acid: dihydrogen phosphate. HPO42-. These form according to the following equilibria. and at low ionic strengths. the aqueous redox potential was controlled by the partial pressure of hydrogen.(aq) + H2O(l) ← HPO42-(aq) + OH-(aq) → PO43-(aq) + H2O(l) ← H2PO4. These were taken from the compilations by Shock and Helgeson (1988) and Helgeson et al. The phosphate species are less strongly ionized at elevated temperature. which are written as reactions with hydroxide for convenience in dealing with alkaline boiler water conditions: H3PO4(aq) + OH. (1978) used in the SUPCRT92 database. H2PO4-.(aq) + OH-(aq) → HPO42-(aq) + H2O(l) ← H2O(l) → H+(aq) + OH-(aq) ← In this work. and phosphate. 1-4 .(aq) → H2PO4.2 The Chemistry of Aqueous Sodium Phosphate at Elevated Temperatures A complete review of the aqueous chemistry of phosphorus has been given by Tremaine et al. Values for the ionization constants of phosphoric acid up to 350°C.EPRI Licensed Material Introduction 1. according to equations 1-1 to 1-4. which was calculated by assuming solubility equilibrium: H2(gas) → H2(aq) ← (1-5) (1-1) (1-2) (1-3) (1-4) Thermodynamic constants for the aqueous phosphate species. The distributions of species are compared in Figure 1-1. PO43-. (1992). are tabulated in Appendix B.

9 4.184 Joules Table 1-3 Maier-Kelley coefficients for heat capacities of solids and gases.9 -58.830 20.0 -5 1-5 .52 7.78 1.7 48.0 39.40 -3.0 0 -32.000 13.88 b x 10 -1 -2 /cal mol K 0.96 34.2 30.000 -53.3 -1.EPRI Licensed Material Table 1-2 Standard state properties* at 25°C and 1bar.600 -8.55 0.0 18.12 -0.560 38.2 44.040 0 -2.6 23.6 -6.5 0 -4.3 30. Species H2(g) O2(g) H2O (l) H2(aq) O2(aq) H (aq) OH (aq) H3PO4 (aq) H2PO4 (aq) HPO4 (aq) PO4 (aq) Na (aq) Fe3O4(s) Fe2O3(s) + 32+ ∆fG° -1 /cal.00 18.3 25.029 16.1 36.274 Cp ° -1 -1 /cal mol K 6.16 23.234 49.60 48.mol K 31.712 13.524 30.4 -32.940 V° 3 -1 /cm .0 * 1 Thermochemical calorie = 4.49 21. Species H2 (g) O2 (g) Fe2O3 (s) Fe3O4 (s) a -1 -1 /cal mol K 6.000 21.0 -114.9 56.9 7.1 25.mol 0 0 18.800 26.3 9.mol 0 0 -56688 4236 3954 0 -37595 -273100 -270140 -260310 -243500 -62591 -242574 -178155 ∆fH° -1 /cal.mol 0 0 -68317 -1000 -2900 0 -54977 -307920 -309820 -308815 -305300 -57433 -267250 -197720 S° -1 -1 /cal.20 3 c x 10 -1 /cal mol K 0.

cal mol-1.7727 -4. c1.4605 -14.3536 a3 0. ω.8691 2.Introduction Table 1-4 a HKF equation of state coefficients for aqueous species Species H3PO4 (aq) H2PO4.6114 -0.8390 0 1.3530 c2 x 10-4 1.3003 3.7758 -2. cal K mol-1.7821 -3.0738 6.(aq) PO43.3131 3. cal K mol-1 bar-1. cal mol-1 bar-1.3726 ω x 10-5 -0. a4.4750 27.5823 5.1427 1.2528 a4 x 10-4 -3.4042 -2.285 0 0.8423 3.3363 5.4182 8.7889 a2 x 10-2 12.2527 5.7246 -0. cal mol-1 K-1 .8729 3.7260 0 -2. a3.9810 0 -10.6315 -0. cal mol-1. a2.4875 3.5259 5.9708 14.8239 -2.0654 4.7357 -9.6251 18.3306 0 1.3233 9.3943 Units: a1.0930 2. 1-6 .0594 1.0435 2.9764 -2.(aq) O2(aq) a a1 x 10 8.0857 -9.0417 c1 -17.9103 -26.1800 0 4.2727 6.2200 1.3460 8.(aq) HPO42. c2.1500 35.2924 -3.4397 5.1122 -2.2560 0 1. cal K mol-1.(aq) H2(aq) Na+(aq) H+(aq) OH.2090 0.

7 6 pH 8 10 12 14 Figure 1-1 The distribution of phosphate species at 25 and 300°C at I=0.25 0.00 0 2 4 5.00 0.00 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 300 C o 1. calculated from the -2 data in Appendix A. 1-7 . pH 10 corresponds to an alkalinity m(OH ) = 10 -1 -4 -1 mol.50 -log(Kw)/2 0.Introduction 25oC 1.00 H3PO4 0.50 -log(Kw)/2 0.kg compared to 10 mol kg at 25°C.25 0.75 H3PO4 H2PO4 - HPO4 2- PO4 3- fraction 0. At 300°C.75 H2PO4 - HPO4 2- PO4 3- fraction 0.

Ravich and Shcherbakova (1955) and Wetton (1981). 1981. Na3PO4. (1977). 1981. The solid solution. 1985). (1975). The hideout behaviour of trisodium phosphate differs from these salts in that its solubility decreases with increasing temperature above 120°C.8(H3O)0.Introduction The complex phase behavior of the sodium-phosphate-water system below 100°C has been determined by Van Wazer (1958) and Wendrow and Kobe (1955). Figure 1-4 shows the increase in solubility at sodium phosphate ratios above Na/PO4 >3. Panson et al. Na2.2PO4. (1977) and Marshall (1982) have identified a region of liquid-liquid phase separation at temperatures above 275°C in aqueous sodium phosphate systems with Na/PO4 ratios between 1. The boundaries of the two phase region are plotted as a function of temperature in Figure 1-3. The solubilities of both salts increase with temperature. 1979. so that only some lower hydrated salts and the anhydrous phases remain at temperatures above 100°C. Wetton (1981) and Taylor et al. but is a related sodium deficient solid solution.2PO4. Raman spectra of the highly concentrated and dilute immiscible liquid phases showed that orthophosphates are the main species present Marshall and Begun (1989). 1989). is structurally related to cubic Na3PO4. The hydrated salts become less stable with increasing temperature. NaH2PO4·Na2HPO4 that they found to be an equilibrium phase at 300°C. and it is a stable phase at temperatures up to 350°C (Taylor et al. It apparently dehydrates to form Na5P3O10 and NaPO3 at temperatures between 300 and 350°C (Wetton. 1-8 . exist as metastable phases in water at room temperature. Figure 1-2 shows the aqueous solubility of trisodium phosphate reported by Schroeder et al. 1968). Wetton.8(H3O)0. Na3PO4·12H2O·¼NaOH and Na2HPO4·2NaH2PO4·2H2O.1. (1979) have identified a compound salt. Broadbent et al. The sharp decrease in the solubility of Na2. 1957). (1937). NaPO3. Marshall. 1981). Although pyrophosphate (P2O74-) and other condensed phosphates.0 and 2. as are two complex salts. Morey (1953) has measured data for the solubility and phase behaviour of monosodium phosphate at temperatures up to 620°C. More recent studies have shown that the saturating phase above 200°C is not the expected trisodium salt. Solubility data for disodium phosphate at temperatures up to 350°C have been reported by Broadbent et al. The solubility of “Na3PO4” increases sharply with excess NaOH.8(H3O)0.and trisodium salts are stable at 25°C. these metastable salts hydrolyse to form the stable orthophosphates at temperatures above 100°C (Marshall and Begun. Edwards and Herzog. along with the solubilities of Na2HPO4 and “Na3PO4” from Figure 1-2 and Broadbent’s study. There is no evidence that condensed phosphates exist as aqueous species at equilibrium in hydrothermal solutions below 400°C. leading to conditions that could be very corrosive. Several hydrated phases of the di. and monosodium phosphate undergoes a condensation reaction above 343°C to form the metaphosphate.2PO4 (“trisodium phosphate”) above 120°C has also been observed by other authors (for example.. Na2. Wetton.0 and temperatures above 300°C (Borovaya and Ravich.

1-9 .Introduction Figure 1-2 The solubility of trisodium phosphate in high temperature water as a function of temperature.

00 at temperatures from 200 to 400°C (Marshall.Introduction Figure 1-3 Liquid-liquid and solid-liquid phase boundaries for aqueous solutions of sodium phosphate salts at Na/PO4 mole ratios from 1.00 to 3. 1982) 1-10 .

Panson et al. (1979) identified the equilibrium phases at 300°C and extended the phase diagram by examining solids recovered from dry-out experiments at different solution compositions. (1975).Introduction Figure 1-4 Solubility of trisodium phosphate in aqueous sodium hydroxide (Boroyava and Ravich. in the belief that the pressure-tube damage observed in some power stations was caused by caustic gouging associated with alkaline pH excursions related with incongruent phosphate precipitation during dry-out. Broadbent et al (1977). under controlled partial pressures of steam. All these results showed that no excursions to highly acidic or alkaline conditions take place when pure sodium phosphate solutions in the range 2. The “congruent phosphate” control practice that is now in widespread use in the power industry was recommended by Marcy and Halstead (1964). 1968) The incongruent precipitation of Na2.8(H3O)0.8 and the invariant point at 2. extending these measurements to higher temperatures and a wide range of compositions.2PO4 causes excursions to high pH in the Na3PO4-H2O system at sodium phosphate ratios Na/PO4 ≥2. Taylor et al.6 are evaporated to dryness. Panson et al.15. 1955).8 (Ravich and Scherbakova. (1975) suggested that this feature of the phase 1-11 .2<Na/PO4<2. Wetton (1981) used rapid quenching techniques to recover and identify the equilibrium solids formed at 350°C. because the solution composition is trapped between the congruent composition at 2. and Wetton (1981) conducted further solubility studies.

Introduction

diagram could be used as the basis for an improved treatment for boiler water chemistry control, and coined the name “invariant point” phosphate treatment.

1.3 Sodium Phosphate Reactions with Magnetite
1.3.1 Hideout Reaction Products: Sodium Iron(III) Hydroxy Phosphate (“SIHP”) and Maricite
Maricite (NaFeIIPO4) has been identified by Broadbent et al. (1978) in their studies on corroding steel systems. It has since been found in sites of severe corrosion associated with tube failures in fossil utility boilers (Dooley and Paterson, 1994; Dooley et al., 1994; Dooley and McNaughton, 1996). Sodium iron(III) hydroxy phosphate, Na3Fe(PO4)2·(Na2(1-x)H2xO), “SIHP”, is the major iron(III) reaction product associated with sodium phosphate hideout. The compound was first reported in the mid-1970's, from pressure vessel studies on hideout (Economy et al., 1975; Connor and Panson, 1983; Broadbent et al., 1978; Tremaine et al., 1992; Ziemniak and Opalka, 1992 and 1993), and its approximate stoichiometry was inferred from elemental analyses on solid reaction products and hydrothermal solutions during hideout experiments (Ziemniak and Opalka, 1992). It is unstable in water at temperatures below 177°C, and its exact formula and structure were unknown until very recently. In 1996, methods were developed at Memorial University to synthesise maricite and sodium iron(III) hydroxy phosphate at temperatures below 250°C in low pressure teflon cells. The largest crystals (50 - 100 µm) were used to determine the structure of both phases by single crystal X-ray diffraction. The crystal structure of pure maricite was identical to that of the impure natural mineral and yielded no new insights. The structure of SIHP, which is described in Section 3, revealed that sodium iron(III) hydroxy phosphate has the formula Na3Fe(PO4)2 · (Na2(1-x)H2x O), with x = 0.22 in the crystal used for the study. This is similar, but not identical, to the formula Na4Fe(OH)(PO4)2 · 1/3NaOH proposed by Ziemniak and his coworkers (Ziemniak and Opalka, 1992). The structure is significant in that it explains the variable stoichiometry observed in powder diffraction patterns, and it identifies the stoichiometry of H and O, which cannot be determined from solubilities or routine methods for inorganic elemental analysis.

1-12

Introduction

1.3.2 Flow and Batch Experiments Under Steam Generator Conditions
Experiments in several laboratories have shown that high concentrations of sodium phosphate react with magnetite under steam generator conditions (Economy et al., 1975; Connor and Panson, 1983; Broadbent et al., 1978; Tremaine et al., 1992; Ziemniak and Opalka, 1992). Flow experiments to determine composition of the sodium phosphate reaction products with magnetite in this laboratory were summarized by Tremaine et al. (1993). Briefly, solutions of sodium phosphate (molality, 0.005 to 0.10 mol kg-1; sodium/phosphate ratio, 2.5 ≤ Na/PO4 ≤ 4.0) were pumped through a bed of finely divided pure magnetite at temperatures from 320 to 360°C at pressures above steam saturation pressure. The uptake or release of sodium and phosphate was determined by monitoring differences in the compositions of the solutions at the inlet and outlet ends of the column. The results, which are consistent with similar experiments by Economy et al. (1975) and Connor and Panson (1983) at temperatures below 320°C, show that hideout occurs when the sodium phosphate concentration exceeds the solubility threshold at which magnetite reacts to form one or more reaction products. The reactions are reversible, and the reaction threshold decreases with increasing temperature. Since phosphate is precipitated preferentially, the aqueous phases become more alkaline during hideout and more acidic when the reaction products redissolve. The observations of sodium phosphate hideout at high temperature, with the accompanying caustic excursion, and the release of phosphate to produce more acidic solutions when the temperature was lowered, are very consistent with operator observations at fossil utilities during hideout incidents. It has proved possible to recover the products from the reaction of magnetite by using a simple batch reaction vessel that allows the reaction products to be filtered and isolated from the solution at elevated temperatures (Tremaine et al., 1992 and 1993). The stoichiometry of the hideout product mixtures observed in the flow experiments matches those from the batch vessels. The results, as determined by powder X-ray diffraction, are summarized in Figure 1-5.

1-13

Introduction

A que ous N a/P O4 < 2.5 32 0o C an d 360o C

N a F eIIP O 4 F e II F e 2 IIIO 4 A que ous N a/P O4 ≥ 2.5 32 0o C

N a 3 F eIII(P O 4 ) 2 .(N a 2.2x H 2xO )

N a 2.6 F e0.2 II P O 4 F e II F e 2 IIIO 4 36 0o C

N a 3 F e III(P O 4 ) 2 .(N a 2.2x H 2xO )

H 2 (a q) F e II F e 2 IIIO 4

N a 3 F e III(P O 4 ) 2 .(N a 2.2x H 2xO )

Figure 1-5 Sodium phosphate hideout reactions with magnetite at 320 and 360°C from flow experiments (Tremaine et al., 1993). At 360°C the reaction to form SIHP oxidized magnetite to produce H2 at ratios Na/PO4 > 2.7.

At 320°C, the hideout reaction at sodium/phosphate ratios Na/PO4 < 2.5 yielded the iron (II) and iron (III) products maricite and sodium iron hydroxyphosphate, 3 Fe3O4(s) + 15 HPO42-(aq) + 29 Na+(aq) → ← 3 NaFeIIPO4(s) + 6 Na3FeIII(PO4)2. (Na4/3H2/3O)(s) + OH-(aq) + 5 H2O(l) Higher ratios, Na/PO4 > 2.5, appear to favour the formation of a solid solution of iron(II) in cubic γ Na3PO4 as the stable iron(II) phase according to the reaction:

(1-6)

1-14

and by the presence of both maricite and SIHP.1). Those from reagents with Na/PO4 = 3. (Na4/3H2/3O). Na3FeIII(PO4)2.+ 2 OH. (Na4/3H2/3O)(s) + 3/x Na3-2x Fe x PO4(aq) + (2 + 3/x) H2O (1-7) The solid solutions formed by Tremaine et al.→ ← III II 6 Na3Fe (PO4)2.3 Thermodynamic Data From Solubility Studies The determination of meaningful thermodynamic data for Reactions 1-7 and 1-8 is complicated by the need to control the hydrogen concentration.3. it was possible to measure the molality of sodium and phosphate in equilibrium with magnetite and SIHP. Na3-2xFeIIxPO4 was only a minor product relative to the iron(III) hydroxyphosphate. at 350°C. The reaction products observed at 350°C were similar to those observed at 320°C. or hematite and SIHP. Ziemniak and Opalka (1992 and 1993) have reported results for the solubility of SIHP in equilibrium with magnetite according to Reaction 1-8. by sampling the aqueous phase. Quinlan (1996) avoided the need to measure redox potentials by carrying out the solubility measurements on SIHP in equilibrium with an excess of hematite. the ferrous iron in the magnetite is oxidized according to the reaction.Introduction 3 Fe3O4(s) + (20 + 9/x) Na+(aq) + (12 +3/x) HPO42-(aq)+ (3/x . at 1-15 .2.4) OH. Its presence as the major product indicates that no reaction with magnetite took place at ratios Na/PO4 ≥ 4. 2 Fe3O4 + 26 Na+ + 12HPO42.0. Two laboratories have attempted to make solubility measurements on SIHP in stirred reactors. This is an important difference because it indicates that. Hydrogen concentrations were not measured and estimated values for the redox potential were used in the thermodynamic calculations. except that the cubic solid solution. the temperature of the vessel was increased in a stepwise fashion and. (1993) from the reactant mixture with Na/PO4 = 3. (Na4/3H2/3O) + H2 + 4 H2O ← (1-8) The solubilities of SIHP and the cubic solid solution were observed to decrease with increasing temperatures.0 were consistent with values of x ≈ 0. 1. Orthorhombic α Na3PO4 is the stable low temperature phase of γNa3PO4. according to the reaction 3 Fe2O3(s) + 26 Na+(aq) + 12 HPO42-(aq) + 2 OH-(aq) → ← 6 Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 5 H2O (1-9) In both studies.5 were consistent with a much lower Fe(II) content (x < 0.→ 6 Na3FeIII(PO4)2.

Ziemnik and Opalka did not control or measure the redox potential.4 The EPRI Project 1.1 Project Objectives and Workplan The goal of this project is to derive a thermodynamic model for describing the major hideout reactions of aqueous sodium phosphate with magnetite and other iron oxides under fossil boiler operating conditions. (ii) 1-16 .Introduction temperatures above the reaction threshold. were estimated. entropy (S°). and heat capacity (Cp°) of SIHP.4. Ziemniak and Opalka used a similar approach based on a simple extended Debye-Hückel equation. Fe2O3(s) and the aqueous phosphate species. a(H 2 O )5 a(Na+ )26 a(HPO 2. for maricite in the literature.)12 a(OH .)2 4 K= (1-10) from which the Gibbs energy of formation (∆fG°). There are shortcomings in both models. Each of these studies derived a thermodynamic model for the formation of Na3Fe(PO4)2·(Na4/3H2/3O)(s) from the solubility results by using known thermodynamic data for Fe3O4(s). 1. To determine new solubility data for SIHP at low sodium phosphate ratios (Na/PO4 < 2. Quinlan’s data was obtained at very high sodium phosphate ratios. Quinlan used activity coefficients of aqueous sodium phosphate estimated from the approximate model proposed by Lindsay (1989.1990).5) and to refit the data determined by Quinlan (1996) to the new speciation model . The proposed workplan included three major experimental tasks: (i) To obtain solubility data for maricite under controlled redox conditions and fit a speciation model to the new data. There are no reported measurements on the solubility. Samples of the solid were recovered to confirm that the reaction product was SIHP. or other thermodynamic data. and the effect of ionic strength on speciation was not adequately considered. to derive values for the equilibrium constant for Reaction 1-9.

then combining these with high temperature solubility data to obtain a complete thermodynamic model of the solubility equilibria. 1996) by measuring the solubility of SIHP in equilibrium with hematite.4. 1996. Solubility products for SIHP have been determined from 225 to 320°C (Quinlan. but at initial sodium phosphate ratios below 2.Introduction (iii) To obtain the calorimetric data needed to extrapolate solubility results for both maricite and SIHP to higher and lower temperatures.2 Calorimetric Data for Maricite and Sodium Iron (III) Hydroxy Phosphate The objective of this task is to determine thermodynamic constants for maricite and SIHP required in the curve fits by independent calorimetric measurements. 1. also at Memorial University. These experiments are reported in Section 4. This approach eliminates the need to make difficult analyses of low concentrations of aqueous iron (III). there is a need to determine the redox potential by measuring the solubility in solutions containing a known molality of dissolved hydrogen. and the effect of ionic strength on speciation was not considered. Maricite and SIHP were synthesised hydrothermally using the procedures developed at Memorial University (Quinlan. The new results and Quinlan’s data have been analysed with a speciation model consistent with that in MULTEQ (Lindsay. Because maricite is an iron(II) phosphate and must be equilibrated with magnetite. 1996. 1996) were obtained at very high sodium phosphate ratios. Tremaine et al. Bridson et al. Because the calorimetric data are required to model the solubility results.4.5.. so that the sodium phosphate solubility equilibria with magnetite can be modelled with fewer parameters. In this study solubility data for the SIHP-hematite system have been measured in a 450 mL hastelloy stirred reactor using identical techniques. a discussion of this task follows . Heats of solution were measured in a CSC 4400 isothermal calorimeter at 25°C. Similar measurements on maricite are much more difficult.. 1998). 1-17 . 1. Heat capacity functions from 25°C to 400°C were measured in a Seiko Differential Scanning Calorimeter. The number of solubility experiments and the overall uncertainty can be significantly reduced by determining the heat capacity functions and heats of solution of solid maricite and SIHP.3 Solubility Experiments on SIHP Previous data for SIHP in equilibrium with hematite (Quinlan. 1988 and 1990). The results are presented in Section 3.

that incorporates the results of the solubility studies and the calorimetry experiments on SIHP and maricite in the presence of magnetite or hematite as a function of the aqueous sodium phosphate ratio. These are presented in Section 6.4. 1. according to the reaction 3 NaFePO4 (s) + 3OH. Solubility diagrams and approximate Eh-pH diagrams for these hideout reactions were calculated and a limited number of experiments to confirm these calculations have been carried out. the solubilty of maricite in equilibrium with magnetite has been carried out in a 450 mL hastelloy stirred reactor. These are extremely difficult experiments because of the corrosive nature of phosphate on hastelloy and the need to manipulate high pressure hydrogen. 1993) there are no reported data in the literature on the solubility of NaFePO4(s).(aq) + H2O → Fe3O4 (s) + 3 Na+ (aq) + 3 HPO42.5 Thermodynamic Modelling: The final product of this work is an equilibrium constant model based on the HelgesonKirkham-Flowers database and Lindsay’s (1990) version of the Miessner activity coefficient model used in MULTEQ.(aq) + H2(g) ← (1-11) A known overpressure of hydrogen was required to control the redox potential of the maricite solubility equilibrium and to suppress the formation of SIHP.4 Solubility Experiments on Maricite Except for the flow studies at 325 and 360°C (Tremaine et al.. temperature and redox potential in the solution.Introduction 1. 1-18 . The results are presented in Section 5.4. In this project.

and 0. The CO/CO2 mixture was also obtained through Canadian Liquid Air.0 µm for hematite. and then dried under vacuum for two days at room temperature to yield a pale green polycrystalline powder.1. The beige-coloured product was ground and washed with water and methanol. The commercial magnetite was shown by powder X-ray diffraction to contain a minor amount of maghemite-Q (γ-Fe2O3).2 µm and 0. 99+%) and NaOH (BDH. 1996). Quinlan.2 .. 1996). The powder XRD pattern after this treatment only showed magnetite.6 -1.2 Calorimetric Measurements Both SIHP and maricite were synthesized by the hydrothermal methods developed by Quinlan (Bridson et al. Hydrogen gas used for the solubility experiments was purchased through Canadian Liquid Air (99. Fe3O4 (Aldrich.95% purity. The particle sizes were 0. 99+%) and magnetite. 98%) were analyzed by SEM.1 Chemical and Materials 2.1. ACS Reagent Grade). 1998. Maricite was prepared by the hydrothermal decomposition of aqueous iron (III) nitrilotriacetate. FeNTA. used as received. Solutions were prepared in units of molality to simplify high temperature solution calculations. The XRD pattern of this product was 2-1 .0 µm for magnetite. Fe2O3 (Aldrich. The reduced sample was quenched by sliding the boat out of the furnace into the cold end of the tube while still under the flowing gas stream. with Nanopure water (resistivity>18MΩcm). The entire assembly was placed in a tube furnace (ThermoLyne 21100) and left at 610°C for two days. This was reduced to Fe3O4 by heating in CO/CO2 gas mixture (11%/89%) flowed at slow rate.1 Solubility Studies Sodium phosphate solutions were prepared from reagent grade Na2HPO4 (Aldrich. Hematite. The reaction was carried out at 225°C for seven days. 2000 psi) in 40 L cylinders.1. 2. ACS Reagent Grade.EPRI Licensed Material 2 EXPERIMENTAL 2. followed by in situ filtration at the reaction temperature (Quinlan.

.020 and Fe/PO4 = 1.0%). The XRD pattern of this sample matched that calculated from single crystal data (Bridson et al. 99.015 ± 0. 1977. NaH2PO4. then recovering the product by in situ filtration at high temperature (Bridson et al. Bridson et al. 1998).00/2.010. presented below. FePO4. Samples were prepared by dissolving two samples of each compound in a 1:1 mixture of concentrated HCl + HNO3 (~ 2 weight percent HCl.03. 1996).378 ± 0. FePO4. Elemental analyses was performed by inductively-coupled plasma emission spectrometry (ICPES). The concentration of H3PO4(aq) was analyzed by titration against a standard NaOH(aq) solution.35±0. x ≈ 2).00) at 250°C for three weeks. NH4Fe(SO4)2. NaOH (BDH. The following ACS Reagent-Grade sodium phosphate compounds were used in the synthesis: Na2HPO4 (Aldrich.01 ± 0.. The SIHP sample was synthesized by reacting FePO4 with the stoichiometric amount of aqueous Na2HPO4 and NaOH (Na/Fe/P =4. consistent with the formula Na3Fe(PO4)2. The thermochemical calculations. the detection limit is estimated to be ≤1 mol percent. 99%).02. in 400 mL of deionized water for one hour. washed with cold deionized water and dried in air overnight.3/1. SIHP. ACS Reagent Grade) with 8 g of H3NTA. using an ARL 3520 DES ICP spectrometer. and it is essential to confirm the Na/PO4 ratio. nitrilotriacetic acid (Aldrich. 2 weight percent HNO3).12H2O (BDH. 2-2 . 99%). Assuming the deviation in the result for Na2HPO4 reflects systematic bias yields Na/PO4=4. Na/PO4 = 4. Na/PO4 = 2.02)O).EPRI Licensed Material Experimental identical to that of maricite in the JCPDS database (LePage et al. Iron nitrilotriacetate (FeNTA) for the maricite synthesis was prepared by boiling 20 g of ammonium ferric sulfate.(Na(1. The absence of iron oxides in both maricite and SIHP was confirmed by the absence of the major reflections for Fe3O4 and Fe2O3 in the X-ray powder diffraction patterns.35±0. The concentration of HClO4(aq) was determined by titration against TRIS. are very sensitive to the stoichiometry of SIHP.00 ± 0.2H2O were analyzed as controls.xH2O. The following results were obtained from the average of the four analyses: Na2HPO4.2H2O (BDH. respectively.2H2O.. and hydrated FePO4 (Johnson-Matthey. 1998). All solutions were prepared from Nanopure water (resistivity>18MΩ cm).02)H(0. Standard solutions of HClO4(aq) and H3PO4(aq) were prepared from the Fisher “Certified” ACS grade products.0101. The SIHP sample was dried at 300°C for 10 hours before use. 1998.020. Samples of Na2HPO4 and FePO4. Fe/PO4 = 1. and diluting duplicate aliquots of each solution by mass to ~ 10 to 50 µg g-1 in sodium and phosphate. 99+%). The resulting yellow-green solid was suction filtered.65±0. Quinlan.

Measurements on SIHP/magnetite and maricite/magnetite solubilities require control and measurements of the equilibrium hydrogen partial pressure. filtering the samples was difficult and some carry-over of particulate material was often encountered at the beginning of the sampling procedure. To provide more precise measurements of pressure the standard pressure transducer system was replaced by an Omega PX-305-5KGI pressure transducer (0. A filter. The Parr 4842 PID temperature controller provided temperature control to ± 1°C. Stirring speed was controlled with a variable motor. A high pressure cutoff. and monitored with a digital tachometer. Several modifications were made to the standard reactor to increase its suitability for this project. cylinder. causing premature rupture. respectively. since no redox equilibria are involved. Sampling of the liquid phase was accomplished though a 0. provided an additional safety mechanism to protect against an unexpected pressure buildup. was connected to the inlet of the liquid sampling tube inside the vessel. reducing deposition of solids. The methodology for making these measurements with a hydrogen overpressure is described in the following section. consisting of a modified 0.25 in Swagelok union containing several layers of 316 stainless steel 325 mesh.25% full scale accuracy) and an Omega DP-25-E process meter.2. The Parr 4562 Mini-Reactor is rated for a maximum pressure of 207 bars and temperatures up to 350°C. The reactor head was equipped with a gold lined rupture disk to prevent corrosion. and all inner parts were constructed of Hastelloy C for corrosion resistance. A schematic diagram of the reactor system is presented in Figure 2-1. Due to the small particle size of the magnetite and hematite. and was equipped with two high temperature cutoffs to prevent temperature excursions. The measurements on the SIHP/hematite were relatively straightforward.2 Solubility Apparatus 2. The head. A wider and lower impeller was also designed to provide increased agitation. The temperature and pressure were recorded during each run by an HP 7231 A recorder.EPRI Licensed Material Experimental 2. and a full description of the equipment and methodology is given by Quinlan (1996). 2-3 .125 in Hastelloy C tube.1 Stirred Reaction Vessel A 450 mL Model 4562 Parr Stirred Mini-Reactor with a proportional-integral-derivative (PID) temperature controller (Model 4842) was used to determine the solubility of both SIHP and maricite in equilibrium with hematite and magnetite. equipped with a condenser located just before the liquid sampling valve.

2 Modifications for Use With Hydrogen. The following safety features were used when operating the system: 2-4 . 10.d. 2.000 psi connected the outlet of the regulator to the valve on the head of the stirred reactor so that the vessel could be charged with an overpressure of hydrogen. so that the solid reaction products formed with magnetite or hematite contained in the trap were left exposed in the steam phase as sampling lowered the level of liquid phase during the course of each run. configured for studies with hydrogen It is important to recover the equilibrium solid phase under conditions which avoid contact with liquid water while the pressure vessel is cooled. 2000 psi commercial gas tank equipped with a Tescom Regulator (Model # 44-1126-24-044.000 psi inlet and outlet pressure). A 1/16 in o.EPRI Licensed Material Experimental Figure 2-1 Schematic diagram of the Parr 450 mL stirred reactor. This was accomplished by fixing a trap made of 100 mesh 316 stainless steel to the cooling water supply tubes approximately at 2/3 height from the bottom of the reaction cylinder. stainless tube rated to 10. The hydrogen gas was supplied from a 40L. and connected as shown in Figure 2-1.2.

except where otherwise noted. The samples were diluted by mass to approximately 50-250 ppm in sodium and phosphorus before analysis. 2. When each run was completed. Before each batch of samples was analyzed.3. 100 and 200 ppm sodium and phosphorus.3 Analytical Methods 2. SS-21RF4) was installed after the standard shut off valve of the regulator. 2-5 . 100 mA and a scan rate of 10° (2θ) per minute.1 Powder X-Ray Diffraction Solid products were analyzed using a Rigaku RU-200 X-ray diffractometer (XRD) with a 12 kW rotating anode Cu Kα X-ray source and a diffracted beam monochromator. A spark-free motor supplied by Parr was used to drive the magnetically coupled stirrer. three standard solutions were run at concentrations of 0. The 3-point calibration curve was fitted by a simple quadratic equation. (ii) (iii) 2. followed by another 100 ppm standard solution. Two samples of deionized water were measured to establish a baseline signal. Before each sample was measured. The spectrometer was controlled by Plasma Vision 60 software. These concentrations were then used to calculate the original sodium and phosphate concentrations before the solutions were diluted. Methanol was added and the resulting mixture was transferred to a slide and placed under a lamp to dry. the raw data was imported into a Lotus 123 spreadsheet where it was converted to concentrations of molality.3. Samples were prepared by grinding to a fine powder with a mortar and pestle. To reduce the flow rate of hydrogen.EPRI Licensed Material Experimental (i) The vessel was contained in a fume hood with an alarm to ensure that it was not shut off. was used to identify the XRD powder patterns from our samples. the solution was flushed through the system for approximately one minute to eliminate contamination error.2 ICP Emission Spectroscopy An ARL 3520 DES ICP spectrometer at the Newfoundland and Labrador Department of Mines and Energy was used to analyze liquid samples taken from the stirred reactor. The diffractometer was operated at 40 kV. equipped with the MDI Jade+ search-match algorithm. and samples were injected by a Gilson Model 222 sample changer. a metering valve (Swagelok. The 100 ppm standard was also analyzed after every ten unknown samples to detect any drift in the response of the equipment during the analysis. A current software version of the JCPDS database.

a method for recovering some solid reaction product for analysis was necessary. Tremaine et al.05-2% of the expected concentrations of phosphorus. and 0. the partial pressure of hydrogen in equilibrium with the reaction products. and because hydrates may form with other reaction products. display a hysteresis in the pressure reading that undoubtably arises from friction in the piston of the fluid-filled fitting that isolates the transducer from the gases in the stirred reactor. for example maricite. after each run. the powder patterns of the solids obtained from the bottom of the vessel showed almost no maricite or SIHP. Finally. the pressure was first increased by heating the solution or adding hydrogen gas in the system up to a maximum value (typically 1500-1700 psi) and then the pressure was allowed to decrease as the reaction proceeded. the results for identical samples agreed within ± 2%. 1977.1-4% of the expected sodium concentrations. For most of the samples. For the maricite measurement it was also essential to measure. The pressure detection system in the head of the stirred reactor was tested by pressurizing the system with nitrogen gas against Omega PX951 pressure transducer traceable to NIST standards and an Omega DP41-E process indicator.4 Solubility and Kinetic Measurements in the Stirred Reaction Vessel 2. as accurately as possible. up to five known standard solutions were included in each batch of unknown solutions as a second check. The results showed that the ICP ES measurements were within 0. 1983). The results of the calibration.1 Experimental Design The experiments were designed to synthesize the equilibrium sodium iron phosphate phase of interest. the solid phase was isolated and analyzed by X-ray diffraction..EPRI Licensed Material Experimental Besides the previously mentioned standardization procedure. then to sample the liquid phase and analyze the concentration of sodium and phosphors by ICP ES.4. Problems associated with recovering the equilibrium phosphate phases are formidable (Taylor et al. in an aqueous medium with known partial pressure of hydrogen. so that the equilibrium reaction product was isolated from the liquid at high temperature. Normally. All the pressure readings were in the range 500-1000 psi and 2-6 . The trap shown in Figure 2-1 allowed a solid sample to be recovered from a region above the level of the residual solution left in the vessel after measurements were complete. During each experimental run . Each sample was diluted to give three aliquots within the range 100-200 ppm in P. To confirm that the correct phase was being synthesized in the stirred reaction vessel. shown in Figure 2-2.. while the solids from the trap and propeller shaft of the stirrer were a mixture of maricite and magnetite. SIHP is not stable in water below 177°C (Connor and Panson. 1993) because one of the expected iron (III) phases. 2. thereby preventing dissolution or rehydration.

Figure 2-3 shows results from a typical set of measurements (Quinlan. and thus corrode the vessel. but to remain unsaturated with respect to the nickel-phosphate reaction product. but large increases in temperature at some certain Na/PO4 ratios could supersaturate the solution enough to cause the formation of the nickel-phosphate reaction product. 1996). which meant that the correction always had the same sign and is approximately the same value. Figure 2-2 Pressure calibration curves showing hysteresis in the pressure transducer response due to friction in the piston-cylinder isolator. Hastelloy C is largely composed of nickel. The iron reaction is more favorable. Since the temperature and Na/PO4 ratio were maintained within these limits.EPRI Licensed Material Experimental were corrected using the hysteresis curve Figure 2-2.1996). and as such it can be very reactive with phosphate under suitable conditions (Quinlan. this problem could essentially be avoided. The partial pressure of hydrogen was calculated from the difference between the total pressure and the saturation pressure of water at the temperature of interest. The temperature of the stirred reactor was raised in a manner that allowed an initially unsaturated solution of known Na/PO4 ratio supersaturated to react with an excess of iron oxide to form the iron-phosphate reaction product. 2-7 .

In Hastelloy vessels. obtained by stepping up the temperature in a stirred batch reactor. 2-8 . the steps must be small enough to avoid crossing the reaction threshold with nickel (Quinlan.EPRI Licensed Material Experimental Figure 2-3 Solubility data for SIHP in equilibrium with hematite. 1996).

the reaction vessel was charged with hydrogen by allowing hydrogen gas at a pressure of 1800-2000 psi to flow into the reaction vessel for 2-3 min without turning off the stirrer. (1984). After 1-2 hours. The ratio was higher in the saturated solutions because the reaction to form SIHP preferentially depleted the solutions of phosphate so that the equilibrium solutions at 300°C had very high Na/PO4 ratios (typically Na/PO4 = 4 to 6). the reaction vessel was usually charged with hydrogen again. 2.15. The full set of results from this project and Quinlan’s thesis (with permission) were used in the analysis. To determine the time required to reach equilibrium. when the temperature and pressure had stabilized.0.1 Kinetics The kinetics for the formation of maricite are more complex than those of SIHP (Quinlan. 1996) because dissolved hydrogen participates in the reaction. Approximately 28-30 g of sintered magnetite was placed in the hastelloy vessel along with 200mL of 0. 1996).0 at 200°C.3 Measurements on Maricite. two kinetic runs were performed at 237°C. Quinlan’s measurements used initial Na/PO4 ratios of 2. Quinlan carried out comprehensive measurements on SIHP at high Na/PO4 ratio from 200 to 300°C. The hydrogen supply line was shut off while the reaction was allowed to continue under isothermal conditions. The maximum allowable mass of water in the vessel was determined by calculating the volume after thermal expansion from the steam tables of Haar et al. Full details are given elsewhere (Quinlan. More measurements were made in this study. Tremaine et al..EPRI Licensed Material Experimental 2. so that the equilibrium solutions had ratios in the range 2.2 Measurements on SIHP Measurements on SIHP/hematite mixtures were carried out in air saturated solutions under oxidizing conditions and do not require a knowledge of the oxidation potential of the system. The saturation pressure of water in the solution at the temperature of the experiment was recorded.4. to replace the lost volume of the sample in the reaction vessel and to maintain the same hydrogen partial pressure (and the corresponding hydrogen 2-9 . 2. Samples of 4-5 mL were withdrawn at regular intervals and total pressure was recorded. 1996. The vessel was then assembled and brought up to a temperature sufficient to exceed the saturation index of the reaction product.3. During the collection of each sample.5 and 3. When sampling was complete.08 mol kg-1 Na2HPO4 solution. using an initial Na/PO4 ratio of 2.4.15 < Na/PO4 < 3.4. each lasting for a period of 8 days. the first 3-5 mL of solution withdrawn was discarded to ensure that the sample line was flushed adequately. This excess of magnetite was thought to ensure that all aqueous iron species are in equilibrium with magnetite during the formation of the maricite.

Data from three different measurements are required to determine specific heat capacities with the DSC: these are the differential output signals (heat flux) between the an empty reference container and (i) the empty container. In our subsequent solubility studies.4. The solubility runs were carried out in the same way as the kinetic runs. The experiments were stopped when sample flow became erratic. A large excess of hematite was used to ensure equilibrium between aqueous iron. Samples were contained in open aluminum pans.. Powder XRD analyses of the solid phases were carried out after each run. 1985).5 Calorimetric Measurements 2. The partial pressure of hydrogen was calculated from difference between the total pressure and the measured saturation pressure of water in the solution at the beginning of the run at each temperature studied. and procedures were checked by measuring the heat capacity of polycrystalline sapphire powder from 298 K to 673 K. A 9.EPRI Licensed Material Experimental concentration in the liquid phase) as before the sampling was done. The results are presented in Section 5. the solution samples were diluted for ICP ES analysis.5. suggesting that the liquid level had dropped below the sample tube.93 mg sapphire disk was used as the reference substance. The vessel was heated from room temperature to the temperature of interest then charged with hydrogen and allowed to react for up to six days with constant stirring. Approximately 5 mL of solution was collected to flush the sample line before two 5 mL samples were withdrawn.2 Solubility Due to time constraints. The specific heat capacities of sapphire were taken from JANAF Thermodynamic Tables (Chase et al. the results of the kinetic study at 237°C were used to estimate the approximate equilibrium times under other conditions. 2. Instead. and (iii) the container with the sample of interest. Samples were taken from the bulk solids at the bottom of the vessel and from the trap for powder XRD analysis after each run. The following formula was used to calculate the specific heat capacity of the sample: cps = cpr (Ys / Yr) (wr / ws) 2-10 (2-1) . At the end of every run. hematite and maricite. the reaction was maintained at constant temperature for approximately four to six days before withdrawing samples.3. (ii) the container with a reference substance of known specific heat capacity.1 Heat Capacity Measurements Specific heat capacities were measured using a Seiko DSC 210 differential scanning calorimeter equipped with SSC5300 thermal analysis software. 2. it was not practical to determine the equilibration time at each temperature.

The second is the heat of mixing of H3PO4(aq) in the acidic medium used for the dissolution measurement. because the measurements must be made in acid solutions to dissolve the iron as Fe2+(aq) or Fe3+(aq).EPRI Licensed Material Experimental where cps and cpr are specific heat capacities of the sample and the reference substance. samples were first dried overnight at 300°C. Yr is the difference between the same empty container and the same container loaded with the sapphire reference substance.5. Two measurements are required to determine the heat of formation. In subsequent runs. however these were unsuccessful. respectively. Ys is the difference in the DSC output signals between the empty container and the same container loaded with sample. Analysis with a Raman microprobe confirmed the presence of hematite on samples recovered from the container at the conclusion of high temperature runs. A few attempts were made to measure specific heat capacities at higher temperatures by avoiding oxidation through the use of sealed aluminum pans. The scan rate was 10°C min-1. to allow the polycrystalline solids to dissolve in ~ 50 g of a 0. respectively. The results from these measurements agree with the recent literature data (Sanahuja and Cesari. The first DSC scans for the SIHP samples showed peaks at ~80 and ~120°C and a small decrease in mass (1%) which we attributed to the release of sorbed water.9461 molal solutions of HClO4 (aq). then scanned up to 500°C. Utah). The DSC scans for maricite displayed irregular behaviour at temperatures higher than 200°C.93 mg) and the sample (9 mg ≤ ws ≤ 25 mg).181 molal H3PO4 (aq) solution into 0. and the effects of phosphoric acid ionization are large. cooled . The first is the heat of solution of the solid in a solution of non-complexing acid at a pH sufficiently low to avoid precipitating iron hydroxides. 2. Heats of solution were measured in a CSC 4400 isothermal heat-flux calorimeter (Calorimetry Sciences Corp. heats of solution of NaCl(cr) in water were measured. The calorimeter was calibrated according to the procedure given by the manufacturer. which we attribute to the onset of thermal effects associated with surface oxidation reactions. Heats of mixing were determined in the heat of solution cell by releasing small quantities of a 1. Provo. 2-11 . using the commercial hastelloy cell provided with the calorimeter. The DSC curves from the second scan were used in the calculations. and the scan was repeated.9461 molal solution of HClO4 (aq). To confirm the accuracy of the calibration.2 Heats of Solution The experimental design of the heat of solution measurements is challenging.. The reaction was initiated by breaking a glass slide that covered a sample of ~50 mg of maricite or SIHP. to determine heat of dilution effects. wr and ws are masses of the reference substance (9. 1984) to within the experimental uncertainty.

.

1996). as reported in Sections 4 and 5. cr) AND SODIUM IRON(III) HYDROXY PHOSPHATE (Na3Fe(PO4)2·(Na4/3H2/3O). Sodium iron(III) hydroxy phosphate is a non-stoichiometric crystalline solid. Quinlan. 1996 . Quinlan. first discovered in 1977 (LePage and Donnay.2 to 0.15 K. cr) 3. However. 1998. 1993. NaFeIIPO4. Maricite.Tremaine et al. Tremaine et al. and the enthalpies of formation of both compounds at T = 298. is an ionic crystal whose structure is identical to that of the impure natural mineral. 1998). This section reports the results of calorimetric measurements leading to expressions for the molar heat capacities of maricite and SIHP as a function of temperature. The main structural feature of SIHP is a chain of iron(III) ions linked by bridging oxygens and phosphate bridges. further data for the solid phases are needed to develop accurate thermodynamic models from these results. Tremaine et al. Tremaine et al. Quinlan. Tremaine et al.Tremaine et al. The iron phosphate chains are held together by sodium ions in the ratio 3Na/Fe/2(PO4). 1993. Bridson et al. 1994). 1993. with typical values of x in the range 0. 3-1 . Charge balance with the O2. 1993. Solubility studies have been carried out in the range 200 < t < 325°C (Ziemniak and Opalka. 1998. 1996).1 Introduction Maricite and sodium iron(III) hydroxy phosphate (“SIHP”) are recently-discovered iron(II) and iron(III) compounds(Ziemniak and Opalka. 1996.EPRI Licensed Material 3 ENTHALPIES OF FORMATION AND HEAT CAPACITY FUNCTIONS FOR MARICITE (NaFePO4. SIHP undergoes a reversible transition to hematite and aqueous sodium phosphate in the presence of liquid water at temperatures below about 180°C. 1996. and must be recovered by in situ sampling methods (Ziemniak and Opalka. 1993. Maricite can be recovered from pressure vessel experiments and power station corrosion deposits without special sampling techniques (Bridson et al.bridge between each iron ion is maintained by Na+ and H+ ions located in a relatively open cage in the phosphate lattice.4 (Bridson et al. 1996). 1977). Na3Fe(PO4)2·(Na2(1-x)H2xO). Dooley and Paterson. 1993. Its crystal structure is shown in Figure 3-1.

EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4. cr) Figure 3-1 Crystal structure of SIHP 3-2 . cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).

These results are averages of data from two runs.333)HClO4·(A + 1)H2O}. Cp{Na3Fe(PO4)2·(Na4/3H2/3O). for the dissolution of SIHP.333NaClO4·Fe(ClO4)3·{2H3PO4·(r .181 molal H3PO4(aq) in HClO4(aq) are listed in Table 3-4.9461 molal HClO4(aq) are listed in Tables 3-2 and 3-3. cr}/(J K-1 mol-1) = 171. Na3Fe(PO4)2·(Na4/3H2/3O)(cr) + rHClO4·AH2O = 4.991×10-2 T . cr)/(J K-1 mol-1) = 107.3272 T + 1.0 + 8. cr) 3. and. Cp(NaFePO4.3 Heat of Solution Results The experimental heats of solution ∆expH for maricite and SIHP in 0.538×106/T2 (3-2) (3-1) 3. NaFePO4(cr) + r·HClO4·AH2O = NaClO4·Fe(ClO4)2·{H3PO4·(r -3 )HClO4·AH2O} and. (3-5) 3-3 . The following Maier-Kelley equations represent the experimental data for maricite (295 K ≤ T ≤ 470 K ).9. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).0 + 0. which agree to within 1%. (3-4) (3-3) Data for the heats of mixing of a small quantity of 1. The data correspond to the following stoichiometric reactions for the dissolution of maricite. These correspond to the reaction: H3PO4⋅AH2O+ (rHClO4)·BH2O = H3PO4·rHClO4·(A+B)H2O.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.371×105/T2 . for SIHP (320 K ≤ T ≤ 700 K).7.2 Heat Capacity Results The experimental values for the specific heat capacities of maricite and SIHP are listed in Table 3-1.

1 137.086 g/mol and molar mass of maricite = 173. 3-4 .5 132.6 319.9 133.7 129.5 134.9 128.1 130.2 127.7 346.6 397.3 322.4 304 306.8 131.7 141.3 138.5 343.8 136. 1 calorie / 4.2 399 * Calculated from cp/(J K-1 g-1) using molar mass of SIHP = 362.8 144.3 340.7 124. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).3 359.4 125.8 Na3Fe(PO4)2·(Na4/3H2/3O)(cr) T/K 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520 540 560 580 600 620 640 660 680 700 Cp/(J K-1 mol-1) 290.1 325 328 331 334.5 309 311.8 126.6 140.8 142.6 365.2 123.* NaFePO4(cr) T/K 295 300 305 310 315 320 325 330 335 340 345 350 355 360 370 380 390 400 410 420 430 440 450 460 470 Cp/(J K-1 mol-1) 123.9 353.7 301.8 372 378.1 337.5 139.184 J.9 298. cr) Table 3-1 Experimental values for the molar heat capacities of SIHP and maricite.81 g/mol.1 293 295.5 127.8 143.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.4 130.5 314 316.1 125.4 385 391.

1 67.184 J.97 -123. 3-5 .0731 45.31 1.640·10 4.4609 0. Table 3-4 -1 Heats of mixing for {HClO4(aq.06 -122. average ∆rHΕ(0) = -49.7 -46.760·10 4.8 -47.87 -47.953 0. cr) Table 3-2 -1 Dissolution of maricite in 0.0262 w(HClO4) g 45.aq) g g 0. Ii(HClO4. LN(HClO4.16 2.951 0.935 -196 -195 ∆expH kJ·mol-1 2.17 -123.84 -48.954 0.99 kJ·mol (95% Confidence Interval).7 If LΦ(HClO4.5175 43.aq) and w(HClO4.956 -1 ∆expH ∆rH (I) ∆rH (0)* -1 -1 -1 kJ·mol kJ·mol kJ·mol o o 121 7087 102 5975 204 11964 199 11663 203 11932 93 5457 -48.020·10 -3 r A I 0.22 46.720·10-3 2. aq) = 0.646 r 86.aq) = 0.982 ∆mHE kJ·mol-1 1.0677 0.181 mol·kg )} w(H3PO4.aq) w(HClO4.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.28 m2 -1 mol kg 7.035 0. Ii) -1 = -201 J·mol .290·10 4. 0.956 0.85 -50.0211.57 -49.aq)g g 0.832·10 9.0 -49.04 -3 -3 -3 -3 -2 * α = 0.951 0.652·10 1.91 45.64 -48. αi = 0. Table 3-3 -1 Dissolution of SIHP in 0.08 ± 1.33 45.If) mol kg-1 J·mol-1 0.56 ± 3.s) w(HClO4.0567 0.57 -46. Ii(H3PO4.0323 0.1190 mol·kg .9461 kg · mol HClO4(aq) solutions w(SIHP) g 0.87 -120.22 * w(H3PO4.0 -47.33 45.87 -49.954 0.54 -47.aq) are the masses of solution.752·10 -3 -3 r 348 439 540 A 20406 25759 31686 -1 I 0. 1 calorie ≡ 4. average ∆rH°(0) = -122.951 0.9461 kg · mol HClO4(aq) solutions w(NaFePO4.23 m2 mol kg-1 2.0211.07 -48.0339 0.54 -50.951 ∆expH ∆rHo(I) ∆rHo(0) kJ·mol-1 kJ·mol-1 kJ·mol-1 -126.0213.91 45.1008.9461 mol·kg-1) + H3PO4(aq.9461 mol·kg . αf = -1 -1 0.67 -47.983 0.25 45. 1.08 ∆calcH kJ·mol-1 0.852 43. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).184 J. 1 calorie ≡ 4.7 -50.155·10 1. 1 calorie ≡ 4.937 0.86 -125.1 -125.61 45.3 -123 -125.0333 0.39 kJ·mol (95% Confidence Interval).0407 0.76 * α = 0.184 J.2 -47.

the principal phosphate species is the neutral acid H3PO40(aq). ∆ionH°(I) = ∆fH°(H+. are given by the expressions Ii = m3 and If = 0. To calculate the heat of solution at ionic strength I = If . I) + (1-α)∆fH°(H3PO40. cr) 3.∆fH°(H3PO40. A small degree of ionization takes place.4.3)∆fH°(H+. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).9461 molal HClO4(aq) corresponds to the reaction: NaFePO4(cr) + rH+(aq) + rClO4-(aq) → Na+(aq) + Fe2+(aq) + (1-α)H3PO40(aq) + α H2PO4-(aq) + (r-3+α)H+(aq) + rClO4-(aq) (3-7) The initial and final ionic strengths of the solution.5Σmizi2= [(r+1+α)/r]m3.Lφ(HClO4. I) . I) (3-10) (3-8) (3-9) yields the standard partial molar enthalpy change of the reaction to form H 3PO40(aq) in a predominantly HClO4 medium at ionic strength I: 3-6 . I) + α ∆fH°(H2PO4-. Ii and If.[Lφ(HClO4. I) + (α .∆fH°(NaFePO4.1 Dissolution of Maricite in HClO4(aq) Under the experimental conditions used here. cr) Subtracting the contribution from the heat of ionization according to reaction 3-6. Ii)] so that ∆solH°(I) = ∆fH°(Na+. I) + ∆fH°(H2PO4-. ∆solH(I).4 Enthalpy Calculations 3. ∆expH is corrected for the small change in ionic strength: ∆solH°(I) = ∆expH . I) . according to the reaction H3PO40(aq) → H2PO4-(aq) + H+ (aq) ← (3-6) The experimental heat of solution ∆expH absorbed by dissolving maricite in 0. I) + ∆fH°(Fe2+. If ) . where m3 is the initial molality of HClO4(aq).EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.

387 J·mol-1 may be calculated.075 ± 1. I=0) + ∆fH°(H3PO40. except the iron species. Remembering that ∆fH°(I) = ∆fH°(I=0) + Lφ(I). in Table 3-6. The uncertainties are the 95% confidence limits for the mean of the values in Table 3-2. I) + 3 Lφ(HClO4.aq) was assumed to be zero. I=0) + ∆fH°(Fe2+. Values of Lφ for the perchlorate salts were taken from the compilation by Parker (1965). 1974. cr) = -∆rH°(I = 0) + ∆fH°(Na+.∆fH°(NaFePO4. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O). Pitzer et al. I) .3∆fH°(H+. from which the average experimental value ∆rH°(I = 0) = -49. 1982. Mesmer and Baes. The standard molar enthalpy of formation of maricite was then calculated by combining Eqns 3-11 and 3-12 to yield: ∆fH°(NaFePO4. 310 and 3-12.α ∆ionH°(I) = ∆fH°(Na+. 1982. I) refers to the relative apparent molar enthalpy of the species H3PO40(aq). I) from the heat of solution measurements reported by Berg and Vanderzee (1975) and Vanderzee and King (1979) The value for LφSP(H3PO40. Values for the ionization constant of H3PO40(aq) and ∆ionH°(I) were taken from Mesmer and Baes (1974) and Sweeton et al.Lφ(NaClO4. CODATA Task Group. LφSP(H3PO40. (1974). I) + ∆fH°(Fe2+. along with data from other workers. 1976) and the required standard partial molar properties for the aqueous species at infinite dilution (Wagman et al. which are designated LφST(H3PO4.3∆fH°(H+. cr) ∆rH°(I) = ∆solH°(I) . I) . cr) (3-11) Values for ∆ionH°(I) (Millero et al. for which no literature data were found.aq). I) and Lφ(Zn(ClO4)3. Relative apparent molar enthalpies for these species were estimated by assuming that values in the HClO4 medium were identical to those for the aqueous perchlorate salts at the same ionic strength. and should not be confused with the relative molar enthalpy of stoichiometric solutions of aqueous H3PO4(aq). 1978.Lφ(Fe(ClO4)2. I) (3-12) Here. LφSP(H3PO40. I) . I) + ∆fH°(H3PO40. Larson. I=0) . Shock and Helgeson. I) LφSP(H3PO40. ∆rH°(I = 0) = ∆rH°(I) . Larson et al. 1988. 3-7 . 1977) are known.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4. 1978. These were assumed to be equal to the values determined for Lφ(Zn(ClO4)2. yields the results for ∆rH°(I = 0) listed in Table 3-2. 1982).aq) (Millero et al. Inserting these values into Eqns 3-8. These are tabulated. I=0) (3-13) The relative apparent molar enthalpies Lφ used in the calculation are tabulated in Table 3-5.

8 -1288.355 -7.950 ±0.24 -1142.15 K.0) -1 J·mol -201 -1506 1879 2941 0 - d Lφ/dI(I=1.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4. Table 3-6 0 Standard partial molar enthalpies of formation and ionization of H3PO4 (aq) at T=298.337±0.3 -1288.159 ±0.136 log Q1 I=0.169 * -1.0 log Q1 I=0 -2.042 -1 Salt HClO4(aq) NaClO4(aq) Fe(ClO4)2(aq) Fe(ClO4)3(aq) H3PO4 (aq)* 0 Lφ(I=1. but was not considered to 0 apply to dilute solutions of H3PO4 (aq) in 1 m HClO4(aq).95 -7. log Q1 estimated from Pitzer and Silvester (1976).011 -2.650 -237.145 ± 0.1 log Q1 I=1.830±0. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).875 ± 0.1 -1288.355 -7. (1982) Mesmer and Baes (1974) Millero et al.065 -92.170 -2.150 -2. 3-8 .95 ∆ionH° -1 kJ·mol I=0.15 K Source ∆fH° -1 kJ·mol -1288.50 -17.881 -91.aq) = 657 ± 29 J·mol taken from Millero et al.630 -285.485 ± 0.26±2. (1982) -7.840 ± 0.183 0 ∆fH° -1 kJ·mol 0 -240.1 -1288. I = m(H (aq) + H2PO4 (aq)) ≈ 0.12 mol kg .74 -8. This value was used in these heat of mixing calculations.510 ± 0. cr) Table 3-5 Parameters for heat of solution calculations Species H (aq) Na (aq) Fe (aq) Fe (aq) H3PO4 (aq) H2O(l) 0 3+ 2+ + + ∆fG° -1 kJ·mol 0 -261.6 -1287.58±4.1 ∆ionH° -1 kJ·mol I=1.148 *∆ionH° measured at T=303.573 -7. (1978) Pitzer and Silvester (1976) Shock and Helgeson (1988) Wagman et al. (1978) corresponds to + -1 1 m stoichiometric H3PO4(aq).025 -1.0) -2 J·mol 7.146 -2.050 -2.3 -1288.3 ∆ionH° -1 kJ·mol I=0 -7.630 -8.87 - * Lφ(H3PO4 .300±0.0 Larson et al.691 ± 0.1 -49.

I) + 2α ∆fH°(H2PO4-. I) +∆fH°(H2O) ∆fH°(Na3Fe(PO4)2·(Na4/3H2/3O).83 ± 2. are given by the expressions Ii = m3 and If = 0. according to Eqn 3-8. yields the standard partial molar enthalpy change for the dissolution of SIHP to form H3PO40(aq) in a predominantly HClO4 medium at ionic strength I: ∆rH°(I) = ∆solH°(I) . I=0) = -(-49. I) + (2α .02)O) corresponds to x = 1/3 in the formula Na3Fe(PO4)2·(Na2(1-x)H2xO). Ii and If.2α ∆ionH°(I) = 13/3 ∆fH°(Na+.cr) (3-16) 3-9 .59 kJ·mol-1 3.∆fH°(Na3Fe(PO4)2·(Na4/3H2/3O). cr) Values for ∆fH° used to complete this calculation were taken from the compilation by Shock and Helgeson (1988) and are tabulated in Table 3-5. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).34±0.30±0. where m3 is the molality of HClO4(aq). ∆expH was corrected for the small change in ionic strength. I) + ∆fH°(Fe3+. I=0) .5Σmizi2= [(r+3+2α)/r]m3. Inserting the enthalpies of formation data for the ions into Eqn 3-12 yields the enthalpy of formation for maricite at T = 298.02)H(0.387 kJ·mol-1) + (-240.22/3+2α)H+(aq) + rClO4-(aq) (3-14) Here it is assumed that the experimental stoichiometry Na3Fe(PO4)2·(Na(1. I) + 2(1-α)∆fH°(H3PO40. I) + ∆fH°(Fe3+. The experimental heats of solution ∆expH correspond to the reaction: Na3Fe(PO4)2·(Na4/3H2/3O)(cr) + rH+(aq) + rClO4-(aq) → 13/3 Na+(aq) + Fe3+(aq) + 2(1-α)H3PO40(aq) + 2α H2PO4-(aq) + (r .EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.065 kJ·mol-1) + (-92.22/3)∆fH°(H+. The initial and final ionic strengths of the solution.35±0. I) + ∆fH°(H2O) .63 kJ·mol-1) .65±0. cr) = -∆rH°(I=0) + ∆fH°(Na+. I) + 2∆fH°(H3PO40.571.15 K: ∆fH°(NaFePO4. Subtracting the contribution from the heat of ionization. cr) (3-15) where I = If .075±1.4.2 Dissolution of SIHP in HClO4(aq) The treatment of the data for SIHP is analogous to that for maricite.3(0) = -1. according to Eqn 3-10. I) 22/3∆fH°(H+. Again. I=0) + ∆fH°(Fe2+. I=0) + ∆fH°(H3PO40.1 kJ·mol-1) + (-1288.3∆fH°(H+. so that ∆solH°(I) = 13/3 ∆fH°(Na+.26±2.

f. I=0) + 2 ∆fH°(H3PO40. 3-16 and 3-17.558 ± 3.i)] + r [Lφ(H+ + ClO4-.63 kJ·mol-1) + (-285.3 Heats of Mixing The heat of mixing data in Table 3-4 may be used to estimate the uncertainty associated with the assumption that the effect of LφSP(H3PO40. I) + 22/3 Lφ(HClO4. from which the average experimental value ∆rH°(I = 0) = 122.4. yields the results for ∆rH°(I = 0) listed in Table 3-3.Lφ((FeClO4)3.22/3 ∆fH°(H+.30 ± 0.830 ± 0. 3-10 (3-19) . I=0) + 2 ∆fH°(H3PO40. ∆rH°(I = 0) = ∆rH°(I) . causing first the dilution of H3PO4ST(aq) in a perchloric acid medium. remembering that ∆fH°(I) = ∆fH°(I=0) + Lφ(I).f / m3. I=0) = -(122. cr) = -∆rH°(I = 0) + 13/3∆fH°(Na+.558 ± 3.f) where r is the mole ratio of HClO4(aq) to H3PO4ST(aq).I=0) (3-18) Inserting values for α.f. m3. adding the enthalpy of formation data for the ions into Eqn 3-18 yields the enthalpy of formation for SIHP at T = 298.22/3(0) = -3. I) (3-17) The standard molar enthalpy of formation of SIHP was then calculated by combining Eqns 3-15 and 3-16 to yield: ∆fH°(Na3Fe(PO4)2·(Na4/3H2/3O).f) + Lφ(H+ + H2PO4-.58 ±4. I=0) + ∆fH°(Fe3+. ∆ionH°(I) and Lφ into Eqns 3-8.13/3 Lφ(NaClO4. I) .i)] + αi [Lφ(H+ + H2PO4-.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.830.22/3 ∆fH°(H+.aq) is negligible. then the deionization of H2PO4-(aq) to its new equilibrium value so that: ∆expH = (1-αi)[LφSP(H3PO40. Now.15 K: ∆fH°(Na3Fe(PO4)2·(Na4/3H2/3O). I = 0) + ∆fH°(Fe3+. The experimental heats may be described by the process in which solutions consisting of initial molalities m2.i)] + (αf .(1-αi)m2. I) 2 LφSP(H3PO40.i H3PO4ST(aq) and m3.042 kJ·mol-1) .87 kJ·mol-1 3.990 kJ·mol-1) + 13/3(-240. m3. cr) Again. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).065 kJ·mol-1) + (-49. The uncertainties are the 95% confidence limits for the mean of the values in Table 3-3.(1-αi)m2. m2. I=0) + ∆fH°(H2O) . cr) = -∆rH°(I = 0) + 13/3∆fH°(Na+.LφSP(H3PO40.f) + Lφ(H+ + ClO4-.i HClO4(aq) are mixed.83 ± 5. αim2.f +m3.1 kJ·mol-1) + 2(-1288.αi )∆ionH°(I=αim2.I) . αim2.34 ± 0.990 J·mol-1 was calculated. I=0) + ∆fH°(H2O) .

respectively.EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4.* Species ∆fHo /J mol-1 -3830.83 ± 5. Hence.0 and 7.(1-αi)m2. Table 3-7 Standard partial molar enthalpies of formation at 25°C and 1 bar and Maier-Kelley coefficients for heat capacities of SIHP and maricite.2 89. The results differ from ∆expH by up to 1.f) (3-20) Setting LφSP(H3PO40.αi )∆ionH°(I=αim2.83 ± 2.184 J 3-11 .0 b x 103 /J mol-1 K-2 327.87 -1571. I) and that Lφ for each species depends only on ionic strength.f) + Lφ(H+ + ClO4-.38 -9.f +m3. ∆expH ≈ (1-αi)[LφSP(H3PO40. Nevertheless. because they are sensitive to r.5 kJ·mol-1.αi )∆ionH°(I=αim2. m3.0 107.f +m3.I) .f) + Lφ(H+ + ClO4-. I=1) may be as large as 1.LφSP(H3PO40. yields a calculated value for the heat of mixing: ∆calcH ≈ (r +αi ) [Lφ(H+ + ClO4-.371 SIHP (s) Maricite (s) * 1 calorie / 4.i)] + (r +αi ) [Lφ(H+ + ClO4-.0 kJ·mol-1.i)] + (αf . m3.3 kJ·mol-1.i)] + (αf .(1-αi)m2. the results suggest that LφSP(H3PO40. The values obtained here are approximate.59 a /J mol-1K-1 171. I) = Lφ(H+ + ClO4-. cr) Eqn 3-19 can be simplified by assuming Lφ(H+ + H2PO4-. as in the calculations above. and because they contain a large contribution from the heat of deionization of H3PO4ST(aq). m3. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O).f) (3-21) Table 3-4 lists values of ∆calcH derived from this model. leading to an increase in the uncertainty estimates for the heats of formation of maricite and SIHP to 3. m3.91 c x 10-5 /J mol-1 K 15.f. I) = 0.

(1968). These differ somewhat from the values compiled by Wagman et al. cr) and Sodium Iron(III) Hydroxy Phosphate (Na3Fe(PO4)2 (Na4/3H2/3O). I = 0) and ∆fH°(Fe3+.5 Discussion The values for ∆fH° from the compilation by Shock and Helgeson (1988) in Table 3-5 are largely based on the CODATA compilation (CODATA Task Group. 3-12 .EPRI Licensed Material Enthalpies of Formation and Heat Capacity Functions for Maricite (NaFePO4. are more consistent with experimental determinations of the solubility of magnetite by Sweeton and Baes (1970) and Tremaine and LeBlanc (1980). which were taken from the measurements by Larson et al. It is particularly noted that there are significant differences in values cited for ∆fH°(Fe2+. cr) 3.(1982) in the widely used NBS Technical Note 270. I = 0). The values in the compilation by Shock and Helgeson.1977).

07 0.48 29. by sampling the aqueous phase.kg 0. The initial compositions of the solutions used in the measurements. Samples of the recovered solid confirmed that the reaction product was SIHP.15 * * with the addition of NaOH to obtain this (Na/PO4) ratio.625 (Na/PO4)initial 2.30 volume of solution /ml 250 250 225 m(Na2HPO4) -1 /mol. and those of Quinlan (1996) are listed in Tables 4-1 and 4-2.2 * * 2. it was possible to measure the molality of sodium and phosphate in equilibrium with hematite and SIHP at temperatures above the reaction threshold of SIHP.EPRI Licensed Material 4 SOLUBILITY AND THERMODYNAMIC MODEL FOR SIHP 4.38 30. run # 1 2 10 mass of hematite /g 28. The temperature of the vessel was increased in a stepwise fashion and. Table 4-1 Summary of the initial experimental conditions to determine the solubility of SIHP in this work. the measurements were made in stirred Hastelloy and Zircalloy pressure vessels containing a known amount of sodium phosphate solution in the presence of an excess of finely divided hematite. The experimental solubility results for SIHP obtained in this project are tabulated in Table 4-3. according to the reaction 3Fe2O3(s) + 26Na+(aq) + 12HPO42-(aq) + 2OH-(aq) → ← 6Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 5H2O (4-1) As outlined in Section 2.1 Experimental Results for SIHP The solubility measurements were carried out in equilibrium with an excess of hematite.2 2.5 0. 4-1 .

15 2.kg 0.17 2.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP Table 4-2 Summary of the Quinlan’s (1996) initial experimental conditions to determine the solubility of SIHP.0193 0.44 2.45 2.5605 0.17 2. run # 1 2 mass of hematite /g 25-30 25-30 volume of solution /ml 250 250 m(Na2HPO4) -1 /mol.10 2.15 2. (Na4/3H2/3O) (s) + 5 H2O ← t o / C mtotal(Na) -1 /mol kg mtotal(PO4) -1 /mol kg (Na/PO4 ) in the solid (Na/PO4 ) in the liquid (Na/PO4)initial ≈2.0148 0.14 2.3464 0.0141 0.0217 0.006 0.0106 0.63 3.60 * * * with the addition of NaOH to obtain this (Na/PO4) ratio Table 4-3 Summary of the experimental solubility data of SIHP obtained in this work according to: + 23 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2.0032 2.37 2.0129 0.0058 0.15 2.55 2.22 2.0291 0.16 2.0701 0.26 2.0121 0.31 2.2522 0.47 (Na/PO4)initial 2.31 4-2 .18 2.27 2.0296 0.2 230 258 285 288 300 306 315 315 324 334 0.0046 0.48 0.0445 0.14 2.1414 0.0493 0.35 2.

4..5.2 Kinetics of the Sodium Phosphate-Hematite Reaction Quinlan (1996) measured the rate of equilibration of SIHP formation from the sodium phosphate reaction with hematite in solutions of initial Na/PO4 = 2. Because the reaction was incongruent.0 as more SIHP was formed after each temperature increment.. and up to 303°C at an initial sodium/phosphate ratio of 3. after sodium and phosphate have been allowed to react with hematite to form SIHP are compiled in Table 4-3. 4.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP The measurements in this project were made from solutions with an initial Na/PO4 ratio of ~2.0. When formed from an initial composition of 3.0 when formed from initial composition Na/PO4 = 2. The Na/PO4 ratio in the solid SIHP formed in these experiments can be calculated by mass balance from the initial and final compositions of the solutions. so that the ratio in the equilibrated solutions at 325°C was as high as Na/PO4 = 6. and these were used without correction.2 listed in Table 4-3. The tabulated results are the sodium and phosphate molalities from solutions that were allowed to equilibrate for at least four days.15) the composition of the equilibrium solutions was maintained in the range 2. 1996).3 Solubility of SIHP in Equilibrium with Hematite The compositions of the final equilibrated solutions.15) are also listed in Table 4-3. Together. 4-3 . The Na/PO4 ratios in these solids (Na/P ≈ 2. Similar calculations on Quinlan’s data showed that the reaction products from high Na/PO4 ratios in solution have Na/PO4 ratios higher than the value of Na/PO4 = 2. A simple rate equation based on the Arrhenius equation was derived from the kinetic experiments and used to correct these results (See Quinlan. Quinlan’s measurements were made at temperatures up to 325°C from solutions with an initial sodium/phosphate ratio of 2.1 ≤ Na/PO4 ≤ 3.5. Some of Quinlan’s solubility measurements had been made on solutions that had equilibrated for only 48 hours.2 and. It was not thought necessary to carry out independent kinetic studies for the measurements at Na/PO4 = 2. These are experimental solubility results for SIHP in equilibrium with hematite. 1998. Kinetic experiments approaching equilibrium from above and below at 225°C confirmed that full equilibrium had been achieved in about four days. SIHP is known to be non-stoichiometric (Bridson et al. these three sets of results span most of the temperature and composition range of interest.5.15. the sodium phosphate ratio progressively increased with each temperature increment. Tremaine et al. which was the stoichiometry studied in the calorimetric measurements.0. the final ratios were as high as Na/PO4 = 16. 1993). since this is approximately the same stoichiometry as SIHP (Na/PO4 ≈ 2.

01650 3.973e-3 4.1 0.9997 0.04 0.2364 0.01 0. and m(Na+. Eqn.039 0. A-23. (Na4/3H2/3O) (s) + 5 H2O ← t /C o m(Na ) -1 /mol kg + m(HPO4 ) -1 / mol kg -2 m(OH ) -1 / mol kg - a(H2O) I -1 / mol kg H2PO4 % - PO4 % 3- (Na/PO4)initial≈2.312e-3 0.658e-3 5. Figure 4-2a also includes a comparison of the equilibrium phosphate species calculated from MULTEQ and those calculated from the thermodynamic data in Tables B-1 and B-3.0140 0.0976 0.76 39.9993 0.23 0.0699 0.657e-3 2.380e-3 8.492e-3 4.91 5.05 0.12 42.9990 0.9986 0. m(OH-.634e-3 9.9996 0.0120 0.327e-3 4.9941 0.34 0.49 6.0565 0.915e-3 3.2 231 259 285 288 300 306 315 315 324 334 0.3457 0. m(OH .0127 8.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP The speciation in the saturated solutions has been calculated using the phosphoric acid equilibrium constants tabulated in Appendix B.0492 0.aq) and m(Na . Table 4-4 2+ Equilibrium values for m(HPO4 .354e-3 6.02 0.0443 0. activity of water and ionic strength for Reaction 4-4.9991 0.1335 0.01907 0.9996 0.012 0. + 23 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2.015 0.0289 0.aq).00 4-4 .018 0.068 0.9902 0.aq).42 45.86 12.79 5. Tables B-3 to B-5.05 14.5008 0. The results were found to agree with those calculated from MULTEQ to within ± 5 percent. These differences are within the experimental error and thereafter MULTEQ was used for the speciation calculations.01 0. aq).08 0.786e-3 0.015 0. The equilibrium values for m(HPO42-.0418 0.0103 0.5601 0. The relative fraction of each phosphate species in each of the three data sets are plotted in Figures 41 and 4-2.0275 0.061 0.8412 0.9997 0.0147 0.51 25.aq). aq) and the ionic strength calculated using the MULTEQ software are tabulated in Table 4-4. using the Lindsay activity coefficient model.659e-3 1.42 32.

2 (this work). 4-5 .EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 100 80 species distribution 60 % HPO4 %PO4 32- 40 %H2PO4 20 0 220 240 260 280 300 320 340 temperature / oC Figure 4-1 The relative concentration of phosphoric acid species in the solubility data for SIHP in equilibrium with hematite for (Na/PO4)initial = 2.

0 (Quinlan.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 100 80 species distribution 60 %PO4H %PO4 %PO4H2 40 20 0 180 200 220 240 260 280 o 300 320 340 a) 100 temperature / C 80 species distribution 60 %PO43- %HPO4 2- 40 20 0 180 200 220 240 260 o 280 300 320 b) temperature / C Figure 4-2 The relative concentration of phosphoric acids species in the solubility data for SIHP in equilibrium with hematite for a: (Na/PO4)initial = 2. MULTEQ: (open symbols) from data in Table 4-4. b: (Na/PO4)initial = 3. 1996). 4-6 .5 (Quinlan 1996) : (solid symbols).

For maricite and SIHP. The standard state properties are tabulated in Table 1-2. 1990): γ|z| = [ γ ± (NaCl) ] z 2 (4-3) where Z is the charge of each aqueous species and values for γ±(NaCl) were taken from Meissner’s equations as modified by Lindsay(1989. The objective in fitting a 4-7 . can be estimated. enthalpy of formation (∆aHo). 4. The data for magnetite. a(H 2 O )5 a(Na+ )26 a(HPO 2. Combining equations 4-2 and 4-3 with the ionization constant data and the solubility results yielded values for the equilibrium constant for Reaction 4-1.4. and there is a much larger base of data for other aqueous species and minerals. (1978) and Shock and Helgeson (1988) for the standard state properties of the oxides and aqueous species was chosen for this work. from which the Gibbs energy of formation (∆aG°). 1992). Calculations of standard Gibbs free energies and other thermodynamic constants at elevated temperatures and pressures were carried out with the SUPCRT92 software package (Johnson et al.T° reported by Xiao and Tremaine in Table 3-7 in Section 3 are the only experimental data available.)2 4 (4-4) K= as a function of temperature.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP Equilibrium quotients for the formation of SIHP from hematite in aqueous sodium phosphate solutions according to Reaction 4-1 were calculated from the molalities in Table 4-4 using the equation Q = 1 /{m(HPO42-. the values of ∆fH298oand Cp.. entropy (S°). hematite and the aqueous phosphate species agree with those in MULTEQ to within the experimental error. and heat capacity (Cp°) of SIHP.)12 a(OH . aq)12 m(OH-.aq)2 m(Na+. aq)26} (4-2) The activity coefficients of the aqueous species were estimated from the approximate model proposed by Lindsay (1989.4 A Thermodynamic Model 4.1990).1 Standard Thermodynamic Properties The database reported by Helgeson et al. the Maier-Kelley coefficients in Table 1-3 and HKF equation-of-state coefficients in Table 1-4.

For this study. To develop a new. Eqn A-23. but there are very significant deviations at higher ionic strength (I = 1.2 Activity Coefficient Model As noted above. and that the deviation is progressively larger at higher and lower temperatures. A comparison of the predicted and experimental values from Mesmer and Baes (1974) values for the second ionization quotient of phosphoric acid.1m). It should be noted that the Lindsay model is in agreement with the experimental data at temperatures near 250°C. fully consistent activity coefficient model was beyond the scope of this work. which is based on the use of NaCl as a model substance (See Appendix A).0m). Qγ.4. activity coefficients were required to 325°C over a wide range of ionic strength and. from potentiometric titrations of dilute phosphoric acid solutions in high ionic strengths of KCl(aq) as a supporting electrolyte. 4-8 . although the Lindsay model is not ideal. where: Qγ = γ(HPO42-) / {γ(H2PO4-) γ(OH-)} (4-5) The ageement is quite acceptable for dilute solutions (I = 0. the activity coefficients of the ionic aqueous species and the activity of water were estimated using the Lindsay model. it is the most practical approach available. 4. at two ionic strengths is given in Figure 4-3. The only experimental data for the phosphate species at elevated temperatures were reported by Mesmer and Baes.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP model to the solubility data is to obtain a result for ∆fG298o consistent with both these results and a practical activity coefficient model.

T}/6 where Σiνi ∆aG°i.8 -2.0 -1.8 log Q2γ -1.l)} (4-7) (4-8) 4-9 .2 -0.1) Meissner-Lindsay model (I=1.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP -0.3 Equilibrium Constants for SIHP The procedure for fitting a model based on the Maier Kelley equation to the solubility data for SIHP was as follows.5 ∆aG°T(H2O.0 .0 -100 I = 0.1 .Mesmer and Baes (1974) I = 1.2 -1.aq) .aq) + 12 ∆aG°T(HPO42-. Equilibrium data for the formation of SIHP from hematite in Table 4-4 were used to calculate experimental values for the Gibbs energies of Reaction 4-1 from the usual expression: ∆rG°T(Reaction 4-1) = -RT ln K (4-6) Experimental values for the apparent Gibbs energies of formation of SIHP were then calculated from the expression: ∆aG°T(SIHP) = {∆rG°T + Σiνi ∆aG°i.T = { 3 ∆aG°T (Fe2O3. 4.4.6 -1.0) 0 100 200 300 400 temperature /°C Figure 4-3 Comparison of experimental and predicted equilibrium quotients for the second ionization of phosphoric acid.4 -0.Mesmer and Baes (1974) Meissner-Lindsay model (I=0.6 -0.4 -1.s) + 26 ∆aG°T(Na+.aq) + 2 ∆aG°T(OH-.

mol o ∆aG T(SIHP) -1 /cal.mol o 0.8 186.8 189. (Na4/3H2/3O) (s) + 5 H2O ← t o /C 230 258 285 288 300 306 315 315 324 334 γ± (NaCl) ln(Q) ln(K) Na/P ≈2.3 -106365 -133379 -186165 -197345 -208064 -246239 -254331 -230901 -266935 -281493 -867765 -871511 -878854 -880499 -881280 -887052 -887383 -883478 -888277 -889074 4-10 .6 197.0 182.8 177.5690 0.7 214.4109 0.0 135.3 106.6922 38.5400 0.6 57.3 157.6923 0.6 224.4 139.0 205.9 233.9 197.0 217.5786 0.5938 0.2 ∆rG T -1 /cal.4047 0. Table 4-5 Thermodynamics of SIHP formation according to Reaction 4-4: + 23 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2.3 126.6993 0.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP The results are tabulated in Table 4-5 and plotted in Figure 4-4.2 167.5 121.6889 0.

∆fH°298 and So298.60e+6 -3.298.s) = c1 + c2 T + c3 T-2 .298 . and (S°f. Model I.66e+6 -3.-.58e+6 -1 ∆aGoT.c3 (1/T-1/Tr) -T {c1 ln(T/Tr) + c2 (T-Tr) + (c3 /2)[(1/T)2-(1/Tr)2)]} + V°298.T°(SIHP.pr (p-pr).i) = ∆fS°298(SIHP. ∆aG°T = ∆fH°298 .EPRI Licensed Material Solubility and Thermodynamic Model for SIHP -3.5 (Na/PO 4 )initial = 2.T {c1 ln(T/Tr) + c2 (T-Tr) + (c3 /2)[(1/T)2-(1/Tr)2)]} + V°298. plotted as a function of temperature: -. Cp.i) .Σνi S°298.68e+6 -3.72e+6 -3.pr (p-pr) (4-9) or.54e+6 -3.s) is the entropy of formation of SIHP from the elements. c2 and c3 are the Maier Kelley coefficients for the heat capacity of SIHP.P(SIHP) / J mol -3.74e+6 0 50 100 150 200 250 300 350 temperature / oC (Na/PO 4 )initial = 2.S°298 (T-Tr) + c1 (T-Tr) + (c2/2) (T2-Tr 2) .c3 (1/T-1/Tr) . 2 2 ∆aG°T = ∆fG°298 .-. using the identity (Eqn.T°(SIHP.-.Σνi S°f.64e+6 -3.56e+6 -3.S°298 (T-Tr) + c1 (T-Tr) + (c2/2) (T -Tr ) . Here c1.70e+6 -3.0 Figure 4-4 Experimantal data for the Gibbs energy of formation of SIHP (∆aG°) for ratios from this work and Quinlan (1996). The temperature dependant values of ∆aG°T(SIHP) were then used to determine parameters in the expression (Eqn A-9).62e+6 -3.s) are accurately represented by the 4-11 (4-11) (4-10) . Model II. _____. A-3) between ∆fG°298.s) and Cp.Tr (S°298 . Since ∆fH°298(SIHP.2 (Na/PO 4 )initial = 3.

the data in Figure 4-4 obtained from solutions with different Na/PO4 ratios diverge from one another. S°298(SIHP. the fitted values of ∆aG°T(SIHP.40 kcal mol-1. 4-9 to these data. with ∆fH°298(SIHP.s) fixed is also plotted in the figure. use was made of the fact that the Lindsay activity coefficient model is in very good agreement with Mesmer’s experimental values for phosphate species in KCl as a supporting electrolyte at temperatures in the range 240 < t < 260°C.T°(SIHP. (ii) (iii) To resolve this problem. Clearly. 4-3.27.s) had a different temperature dependance than the trend of the data in Figure 4-4.0 < Na/PO4 < 2. To do this.42 kcal mol-1 and ∆fG°298(SIHP.4. The fit yields the result ∆aG°523(SIHP.22 ± 1. especially at the highest temperatures studied. There are almost certainly errors in the speciation calculations due to uncertainties in the activity coefficients (See Figure 4-3).s ) = -847. one which is fully consistent with the calorimetric data.4 Model I The objective of Model I is to determine rigorous Gibbs energy data for the solid that is free.Tr ∆fS°298.27 that lie in this range. These uncertainties become magnified by the stoichiometry of Reaction 4-1 and the resulting exponential terms in Equation 4-4. Even with this restriction. consistent with the calorimetric data for ∆fH°298(SIHP.s) and Cp.s) should be the only adjustable parameter in Eqn 4-9. Figure 4-5 presents a plot of experimental data for ∆aGT°(SIHP) for solids with stoichiometry 2.s) and Cp.s) can be calculated from ∆fG°298 = ∆fH°298 . two models were fitted to the data. and a second which is a best fit to the entire solubility data set. The least squares fit of Eqn.1 < Na/PO4 < 2.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP parameters in Table 3-7 in Section 3. the model was fitted only to solubility data for solids with 2. as much as possible. from the uncertainties in the activity coefficient model. As a result.15.27 ± 1. There are several reasons for this: (i) The Na/PO4 ratio in solid SIHP precipitated from high Na/PO4 solutions is higher than Na/PO4 = 2. and in Table B-1 (Appendix B).T°(SIHP. These values have been tabulated in Table 4-6. 4.s) in Section 3. presumably because of the systematic errors in the activity coefficients estimated from Eqn. 4-12 .s) = -870. from which ∆fG°298(SIHP.

23 ± 1.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP -3.mol .p (SIHP) / J.-. model II.1 < Na/PO4 < 2. To do so.75e+6 100 150 200 250 300 350 400 o temperature / C Figure 4-5 Experimental data for the Gibbs energy formation of SIHP (∆aG) for solids with stoichiometry 2.59 ± 2.K 80. Model I II ∆fG -1 / kcal.59 ± 1.27 as a function of temperature: -.. The experimental values for Cp.65e+6 -3.99 4.3 183.mol o ∆fH -1 /kcal.T°(SIHP.2 ± 11. over the complete range of the experimental data. ______.4.55e+6 ∆aGT.50e+6 -3.82 -915.70e+6 -3. the constraint that the fit must be consistent with the experimental value of ∆fH°298(SIHP. Table 4-6 Standard state properties of SIHP at 25°C and 1bar.8 ± 0.s) determined in Section 3 must be relaxed. model I.40 -862.mol -1 -3.43 ± 2.40 -824.-.60e+6 -3.1 o -847.-.-.mol o S -1 -1 /cal.s) have been retained in the belief that this constraint leads to a better ability to extrapolate the solubility data to higher or 4-13 .5 Model II The objective of Model II is to determine Gibbs energy data for the solid that will allow a description of the solubility of SIHP using the Lindsay activity coefficient model.

using the original initial compositions as input. the agreement is in fact excellent given the difficult nature of these experiments.s) = -862. 4-14 .99 kcal mol-1 and ∆fG°298(SIHP. Figures 4-6.s) varied and Cp. with stoichiometry Na/PO4 ≈ 2.3. The calculated values OH-(aq).43 ± 2. respectively.T°(SIHP. 4. The test is severe because any asymmetry in the stoichiometry of the SIHP would result in a very different Na/PO4 ratio in the final equilibrated solution when there is a high degree of supersaturation.59 ± 2.2.s) fixed. The larger error arises because m(OH-. total phosphate. The magnitude of the error can be estimated by mass balance from the stoichiometry of the initial solutions and the reaction products. rather than 2.5 Discussion A severe test of Model II is to use it to predict not just equilibrium solubilities. the calculated alkalinity. Figure 4-5 presents a plot of the experimental data for ∆aGT°(SIHP) for solids with stoichiometry 2. These values have been included in Table 4-6 and in Table B-1 (Appendix B). with ∆fH°298(SIHP.2.s ) = -824. the calculated Na/PO4 ratios are too large at the higher temperatures where the real SIHP reaction product had ratios Na/PO4 > 2. The uncertainty in hideout calculations increases with the degree of supersaturation. As expected. is also plotted in the figure. The least squares fit of Eqn. and OH-(aq) respectively.aq) is calculated from the charge balance Na+(aq) and the phosphate species so that both the experimental and calculated values are sensitive to errors in both sodium and phosphate.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP lower temperatures. The agreement for sodium and phosphate is within 35% for the majority of the solutions studied . as shown in Figure 4-10.The accuracy of the equilibrium solution calculations is estimated to be ± 20% for SIHP.82 kcal mol-1. These are the values that should be used in solubility calculations with MULTEQ. 4-7 and 4-8 show the results of “hideout” experiments calculated from Model II using the initial conditions listed in Table 4-1 for SIHP with Na/PO4 ≈ 2. although it must be stressed that they contain errors that compensate for errors in the activity coefficients from which they were derived. from 200 to 300°C. The fit yields the results ∆fH°298(SIHP. the calculated molalities of both Na+(aq) and the phosphate species are low by about 50% and 80%.27 that lie in the range 200 < t < 320°C. 4-9 to these data.5 with values calculated from Model II. are low by about 70% at the highest temperatures. along with the experimental molalities for Na+(aq).15 as used in the model. As a result. but the compositions of the solutions recovered from the pressure vessels in this work (Table 4-3) and by Quinlan (1996). becomes too high by about 50% at 300°C.1 < Na/PO4 < 2. While these errors could be corrected by including SIHP with variable stoichiometry and a more realistic activity coefficient treatment in the model. In addition. Figure 4-9 compares the experimental values for SIHP reported by Quinlan for solution with (Na/PO4)initial = 2. shown in Figure 4-8.

2: solid symbols.0 220 m / mol.kg -1 0.08 m / mol.05 0. open symbols.00 260 280 300 temperature / oC 320 340 Figure 4-6 Sodium molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.03 0. calculated from Model II.4 0.5 0.10 0.3 0.8 0.1 0.2 0. 4-15 .7 0.kg -1 240 260 280 300 320 340 temperature / oC 0.6 0.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 0. experimental.

EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 0.05 0.2: solid symbols. calculated from Model II.030 m / mol. 4-16 .010 0.25 0.20 0.040 0.40 0.10 0.050 0.kg -1 0.020 0.15 0.kg -1 220 240 260 280 300 320 340 temperature / oC 0. open symbols.35 0.000 260 280 300 temperature / oC 320 340 Figure 4-7 Phosphate molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.00 200 m / mol.30 0. experimental.

040 0. 4-17 .030 0.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 0. open symbols.000 260 -1 280 300 temperature / C o 320 340 Figure 4-8 Hydroxide molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.050 0. experimental.060 0.020 m / mol.070 0.010 0.030 0.010 0.2: solid symbols.080 0.kg 0. calculated from Model II.020 0.kg -1 220 240 260 280 300 320 340 temperature / oC 0.000 200 m / mol.

EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 1.5 (b) 0.kg -1 0.4 0. open symbols.2 0.2 (a) 1.6 0.0 0.2 0. 4-18 .1 0.0 210 220 230 240 250 260 o 270 280 290 temperature / C 0.kg -1 0. experimental.5 (Quinlan 1996): solid symbols. calculated from Model II.0 210 220 230 240 250 260 o 270 280 290 temperature / C Figure 4-9 (a) sodium and (b) phosphate molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.8 m / mol.4 0.3 m / mol.

open symbols.5 (Quinlan 1996): solid symbols.EPRI Licensed Material Solubility and Thermodynamic Model for SIHP 0.05 0. 4-19 . calculated from Model II.00 210 220 230 240 250 260 270 280 290 temperature / oC Figure 4-10 Hydroxide molalities of solutions in equilibrium with SIHP and hematite from (Na/PO4)initial = 2.10 m / mol.kg -1 0.15 0. experimental.

.

calculated using the methods outlined in Appendix A (section A. and those determined for SIHP in Section 4. according to the reaction: Fe3O4(s) + 3 Na+(aq) + 3 HPO42-(aq) + H2(aq) → 3 NaFePO4(s) + 3 OH.4. in which maricite was equilibrated with aqueous sodium phosphate. 5-1 .4).EPRI Licensed Material 5 SOLUBILITY AND THERMODYNAMIC MODEL FOR MARICITE 5. following the methods described in Section 2.4.1 Experimental Results for Maricite Experiments to determine the solubility of maricite in equilibrium with aqueous sodium phosphate solutions were carried out in the presence of magnetite and hydrogen. A list of the initial sodium and phosphate molalities is given in Table 5-1. The equilibrium hydrogen pressure was determined by difference from the total pressure in the vessel and the experimental saturation pressure of water. A second set of experiments was carried out. The experimental conditions are discussed below in Section 5.+ H2O ← (5-1) The measurements were made in the Hastelloy 450 mL stirred reaction vessel. Table 5-2 lists typical hydrogen molalities and gas-phase fugacities.2. magnetite and SIHP. The objective of these measurements was to test for self consistency between the thermodynamic constants obtained for maricite through Reaction 5-1.

9986 0.8 120.0 10.0 10.0 125.9927 0.0 2.40 29.9934 1.00 24.60 28.0 2.95 30.0 2.1686 0.9 25.5 1.0 10.0073 0.kg 0.0080 0.0 125.1894 0.0 1.9997 0.0 124.3 4.9914 1.1 109.0 11.0126 0. Table 5-2 Thermodynamic functions of hydrogen in the vapour and aqueous phases.08 0.1710 1.9993 0.04 0.00 volume of solution /ml 200 200 200 200 200 200 200 200 200 200 [Na2HPO4] -1 /mol.9986 0.0 10.08 0.0 10.0000 0.0 125.7 85.0 12.8 18.0974 0.0484 0.9993 0.5 b b maricite did not precipitate.9962 0.0 125.0 10.0 125.0 10.0311 0.9 15.0176 0.0 122.3 14.5 39.3072 a(H2) 0.7 120.0154 0.0 125.9945 0.0090 0.9999 0.9999 0.0 2.5 0.1107 0.00 30.0000 0.8 8.5 69.0 11.0740 5-2 .0 11.0 2.2061 0.0 1.08 0.1463 0.0 ϕ∞(H2) 1.4 ϕ∞(H2) 1.0 2.0 2.08 22.9945 0.80 27. T /°C 25 50 75 100 125 150 175 200 225 250 300 325 psat(H2O) /bar 1.4 95.9976 0.0 124.0 2.0 10.0989 0.0 125.08 0.0 10.0336 p(H2) /bar 10.03 0. with the addition of NaOH.0 125.0 125.3072 a(H2) 0.5 85.08 0.1751 0.9997 0.9927 0.08 0.3 39. prepared using NaH2PO4.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite Table 5-1 Summary of the initial experimental conditions used to determine the solubility of maricite.20 30.0 1.0 10.2 4.06 b b Na/PO4 2.5 35.9976 0.46 31.0 ptotal /bar 11.0902 0.0074 0.5 ptotal /bar 125.0 1.0915 0.0 10.0 125.9962 0.5 p(H2) /bar 124.1710 1.0 125.2 116.0105 0. run # 6-1 to 6-2 7-2 7-4 7-5 7-8 8-1 to 8-6 12-1 to 12-3 14-1 to 14-3 15-1 16-1 a b a mass of magnetite /g 29.8 130.1265 0.5 25.0079 0.5 99.0 125.

sat) are the total molalities of phosphate species at time t and at equilibrium.2 Kinetics of the Sodium Phosphate-Magnetite Reaction Experiments were carried out at 237°C to determine the rate of maricite formation from aqueous sodium phosphate solutions in the presence of magnetite and hydrogen. equivalent to those formed by Fe 3+(aq) with SO42-(aq) which is isoelectronic with HPO42-(aq) (Ziemniak et al. probably through the formation of a surface phosphate complex. 1993). commonly used in mineral dissolution studies (Stumm and Morgan.1) k·a·t + { m(PO4..403 mol-1 kg hr-1 m-2. After an initial overpressure of hydrogen was introduced. t)] n (5-2) where k is the rate constant. Because the kinetic runs were done only at one temperature. however it is noted that the value of n is consistent with a surface activation control mechanism (Stumm and Morgan.m(PO4. Diffusion of HPO42-(aq) to form the adsorbed complex is fast at these temperatures in a stirred vessel. The morphology of the maricite reaction product suggests that it was formed from precipitation from aqueous solution. a simple rate equation. respectively. The parameter n is the reaction order: n = 1 if the kinetics are diffusion controlled. it is useful to speculate about some factors that appear to control the rate of formation of maricite in these experiments. rather than by epitaxial growth. 1970). The results are tabulated in Table 5-3.t) and m(PO4. and 1 < n < 3 if the kinetics are under surface activation control. sat) .sat) + [(n . although the conditions used in the solubility measurements are duplicated.075 mol kg-1.00674 mol kg-1 for an initial concentration of phosphate equal to 0. 1970. a is the oxide surface area. according to Reaction 5-1. The reaction must have been preceded by the dissolution of magnetite.sat) = 0. As a result. While the experimental conditions above are too complex to quantify. was adopted to describe the experimental results: d m(PO4. and the rate-determining step is undoubtedly a 5-3 .. 1992. Blesa et al.m(PO4 . the hydrodynamic conditions and the available surface area for magnetite and maricite could not be well controlled in these experiments. and m(PO4. and m(PO4. The fitted rate constants for Reaction 5-1 at 237°C were k·a = 10.t) = m(PO4 .t) / dt = k·a [m(PO4. The small pressure drop that accompanied the sampling procedure (typically 5 to 10 bars) was reversed by recharging the vessel with hydrogen to restore the total pressure to the value recorded immediately before the sample was taken. Integration at n≠1 yields the expression: m(PO4.t = 0) . a determination of the Arrhenius parameters was not possible.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite 5.sat)}(1-n) ]1/(1-n) (5-3) The kinetic data are well described by equation 5-3 using n = 2 as can be seen in Figure 5-1 where the experimental results are plotted as a function of reaction time. samples were withdrawn at regular intervals. 1994). Clearly.

0295 2.1009 0.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite surface-controlled process.2 1.0355 0.0251 0.3 3.0878 0.9 55.0286 0.0295 0. Blesa and his coworkers (1994) have reviewed recent work on the dissolution mechanisms of iron oxides in considerable detail.0 53.0902 0.3 16.8 25.1 1.3 1. ← Sampling time / h ptotal /bar p (H2) /bar mtotal(Na) -1 / mol kg Run # 1 mtotal(PO4) -1 /mol kg Na/PO4 in liquid Na/PO4 in solid 87 159 90 136 68. access to the surface may be impeded by a surrounding layer of reaction products during latter stages of the reaction.7 1.5 0.7 50. 5-3 5-4 .7 * * Excluded from curve fits to eqn.0877 Run # 2 0.7 47.6 3.0503 0.5 31. Despite the high surface area of finely divided magnetite in these experiments.1 62.1 1.1 1.3 4.2 54.1056 0.0 1.1 23.0941 0.4 4.1023 0.7 31.6 27.1 1.1 0.0386 0.7 3.1 15 39 63 111 165 207 62.1162 0. All these results suggest that equilibration times of 4 days are sufficient to achieve equilibrium at 237°C and higher temperatures.2 19.3 3.8 24.6 58.0931 0.3 2. Table 5-3 Kinetics of maricite formation at 237°C according to reaction 4-1: + 2Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH + H2O.0285 0.0 22.0 3.4 0. Almost no work has been reported on studies in high temperature water.1193 0.8 56.7 36.3 1.0237 3.0206 0.

0 at temperatures between 217 and 300°C.06 0.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite 0.3 Solubility of Maricite in Equilibrium with Magnetite and Hydrogen The solubility of maricite was determined from several runs with initial sodiumphosphate ratios of 1.16 0.10 0. even at the highest temperature studied. With the exception of run 14. Table 5-4 contains the experimental values for the molalities of sodium and phosphate in solution as measured by ICP-ES. The partial pressure of hydrogen was determined as a difference between the total equilibrium pressure at the end of each run and the saturation pressure of water. the experimental design limited increases in the Na/PO4 ratio of the aqueous phase to values below 5.3. and the stoichiometry of the reaction product. The small increase in the partial pressure of water arising from the decrease in the concentration of aqueous sodium phosphate as the reaction proceeded was neglected.5 and 2. 5-5 .kg -1 mtotal(PO4) 125 150 175 200 5.00 0 25 50 75 100 Time / h Figure 5-1 The kinetics of maricite formation at 237°C as evidenced by the decrease in sodium and total phosphate molalities to their equilibrium values after approximately 100 hours.12 0. the partial pressure of hydrogen at equilibrium.14 0. after equilibration times of 4 to 6 days.08 0. the total pressure.0. mtotal(Na) m / mol.04 0.02 0. measured before charging the vessel with hydrogen.

1009 0.4.9 1.4 A Thermodynamic Model 5.1193 0.5 101.7 2.7 3.1 1.0251 0.0 53.1 1.4 3.0186 0.3 45.2 2.9 83.2 1.0931 0.2679 0.0 4.0902 0.0095 0.9 81.1 Equilibrium Constants for Maricite Table 5-5 lists the equilibrium molalities of Na+.0386 0.0295 0.8 24.0476 0. HPO42-.0066 0.2 1.2 2.0 3.5 2. The equilibrium quotient for the formation of maricite from magnetite and aqueous sodium phosphate according to Reaction 5.0399 0.3848 0.8 56.0095 0.3 4.0039 0.9 55.7 13.1 54.9 1.0 5.1010 0.3 1.6 13.7 47.3 5.1 1.2 p(H2) /bar 71.6 4.0086 0.9 3.0295 0.0355 0.1 118.0317 0.0374 mtotal(PO4) -1 /mol kg 0.5 23.2 0.8382 0.7 90.9 55.5843 0.4 4.8 1.0324 0.1 1.4 86.4 mtotal(Na) -1 /mol kg 0.6 27.0 2.6 66.1 0.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite Table 5-4 Summary of the experimental runs on the solubility of maricite according to: + 2Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH (aq) + H2O(l) ← Sample # 6-1 6-2 7-2 7-3 7-4 7-5 7-6 7-7 7-8 8-1 8-2 8-3 8-4 8-5 8-6 12-1 12-2 12-3 14-1 14-2 14-3 15-1 16-1 t /°C 217 217 217 237 237 257 237 237 238 237 237 237 237 237 237 257 257 257 300 300 280 217 237 Sampling time / h 116 236 72 87 159 94 90 136 189 15 39 63 111 165 207 18 90 138 26 45 142 144 144 ptotal /bar 92.0076 Na/PO4 in liquid 2.0 85.0206 0.0285 0.3 3.0098 0.2 48.7 4.1023 0.0503 0.1162 0.0237 0.0450 0.9 1.1 1.0440 0.0941 0.4 5.1 62.2 1.0306 0.3 1.1 23.5 19. H2PO4-.7 46.0877 0.9 48.0286 0.3 1.8 109.9 Na/PO4 in solid 1.8 25.0388 0.8 0.0 22.7 31.1 0.1 62.2 107.1 is defined as follows: Q = m(OH-)3 /{m(Na+)3 m(HPO42-)3 m(H2)} 5-6 (5-4) .1 0. PO43.7 5.4 14.0767 0.1156 0.7 31. the ionic strength and the activity of water calculated by MULTEQ software from the data in Table 5-4.0878 0.7 55.1 0.0323 0.9 50.3 2.5 65.6 58.4 4.3 36.0 3.1059 0.1056 0.7 3.6 3.3 16.2 68.9 10.7 91.and OH-.7 1.

i refers to the sum of the entropies of the elements at 298. ∆fH°298 and So298 (Eqn.S°f.S°298 (T-Tr) + c1 (T-Tr) + (c2/2) (T2-Tr 2) . 5-7 .298. Entropies of the elements were taken from NBS Tables (Wagman et al.298. A-9 with the assumption V°T = V°298 .i). A-3): ∆aG°T(NaFePO4.s) = ∆fG°298 ..T}/3 where Σiνi ∆aG°i.T = {∆aG°T (Fe3O4. A-23).s) = ∆fH°298 . These experimental values of ln Q and ln K are tabulated in Table 5-6.Tr (S°f. takes the following form: ∆aG°T(NaFePO4.s) = {∆rG°T + Σiνi ∆aG°i. as calculated from the expression: ∆aG°T(NaFePO4.aq) .i = 529.1 (p-pr) (5-7) (5-6) (5-8) (5-9) (5-10) where Σνi S°298.298 . The expression for ∆aG°T of maricite. Apparent Gibbs energies of reaction. obtained by integration of Eqn. ∆rG°T(Reaction 4-1) = -RT ln K and the apparent Gibbs energies of maricite formation. aq) .1 (p-pr) or using the identity between ∆fG°298.aq) + 3 ∆aG°T(HPO42-.c3 (1/T-1/Tr) -T {c1 ln(T/Tr) + c2 (T-Tr) + (c3/2)[(1/T)2-(1/Tr)2)]} + ∆aV°298 0.3 ∆aG°T(OH-.15 K forming maricite. multiplied by their stoichiometric coefficients (Σνi S°f.∆aG°T(H2O.aq) + ∆aG°T(H2. 1982).c3 (1/T-1/Tr) -T {c1 ln(T/Tr) + c2 (T-Tr) + (c3 /2)[(1/T)2-(1/Tr)2)]} + ∆aV°298 0.69 J K-1mol-1).298 (T-Tr) + c1 (T-Tr) + (c2/2) (T2-Tr 2) .EPRI Licensed Material Solubility and Thermodynamic Model for Maricite from which the equilibrium constant was calculated K = {a(OH-)3 a(H2O)}/{a(Na+)3 a(HPO42-)3 a(H2)} (5-5) using activity coefficients from the Lindsay model (Eqn.Σνi S°f.l)} are also included in the table.s) + 3 ∆aG°T(Na+.

2 101.1208 0.0224 0.8 2.8 0.0 a(H2) ϕ(H2) a(H2O) m(Na ) -1 /mol kg 0.0214 - H2PO4 % 0. m(OH .9 3.aq).3 1.6 1.0037 0.0201 0.0374 0.0181 0.9975 0.5 84.9 55.1155 0.0476 0.8 6.9 - PO4 % 3- I -1 /mol kg 0.9919 0.3 0. ← sample # 7-2 15-1 7-4 7-8 8-6 16-1 7-5 12-3 14-3 --- t /°C 217 217 237 238 237 237 257 257 280 300* ptotal /bar 107.2 91.8 0.1078 0.0475 0.0287 0.1081 0.9987 0.1369 0.7 48.2 14.6 0.0145 0.aq).0092 0.5 13.1 0.1005 0.1806 0.0767 0.1058 0.9919 0.9983 0.4 0.9989 0.0352 0.6 2.1370 0.5 90.0313 0.0596 0.9978 0.0309 0.5 2.0472 0.7 22.0137 0.0288 0.0650 0.0459 0.9933 0.0353 0.8 0.1496 0.aq) and m(Na .1565 0.9 109.1 62.0390 0.1195 0.0568 0.1 53.5 118.0299 0.1422 0.2 * Excluded from data fits 5-8 .9990 0. activity of water and ionic strength for the maricite formation reaction: + 2Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH (aq) + H2O(l).0870 0.0444 0.0 p(H2) /bar 85.9919 0.1710 0.9971 0.1556 0.9974 0.9932 0.0074 0.9913 0.9992 1.7 31.3 81.4 1.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite Table 5-5 2+ Equilibrium values for m(HPO4 .0633 0.0385 0.3 0.0087 2- m(OH ) -1 /mol kg 0. partial pressure and activity of hydrogen.9974 0.0423 0.0017 1.4 48.9919 0.9913 1.0448 0.0389 + m(HPO4 ) -1 /mol kg 0.7 46.6 0.0310 0.5 1.1190 0.5 3.

one which is fully consistent with the calorimetric data.91 17.66 kcal mol-1.38 ∆rGT / cal 0 ∆aGT (Maricite) -1 / cal mol 0 -14152 -12548 -18891 -18328 -18711 -19531 -20695 -22245 -25445 -24350 -354373 -353838 -356283 -356095 -356223 -356496 -357178 -357695 -359006 ------------ * Excluded from the data fit.6955 0. As was the case for SIHP.6496 0. The least squares fit of Eqn.5658 0.s) = -357.11 7.76 15.64 18. the least squares fit is plotted in Figure 5-2.24 12.6481 0.54 11. two models were again fitted to the data.T°(NaFePO4.Solubility and Thermodynamic Model for Maricite Table 5-6 Thermodynamics data of maricite formation according to reaction 5-1: + 2Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH + H2O.s) and Cp. 5.83 ln(K) 14. ∆fH°298(NaFePO4. 5-10 to these data.11 23.6018 0.88 18.90 12.04 18.2 Models I and II In the first attempt.70 kcal mol-1 and ∆fG°298(NaFePO4.62 14. The objective of Model I is to determine rigorous Gibbs energy data for the maricite and. this discrepancy was assumed to arise from the systematic errors in the activity coefficients estimated from Eqn. again.s) had a different temperature dependance than the trend of the data in Figure 5-2. and a second which is a best fit to the entire solubility data set. 5-9 . Therefore. the fitted values of ∆aG°T(maricite.27 19.6743 ln(Q) 8.T°(NaFePO4. A-23. use was made of the fact that the Lindsay activity coefficient model is in very good agreement with Mesmer’s experimental values for γ± at temperatures in the range 240 < t < 260°C.01 ± 0.97 17. yields the result ∆aG°523(NaFePO4.s ) = -347.5860 0.4. These values have been included in Table 5-7. ← t / °C 217 217 237 238 237 237 257 257 280 300 * γ±(NaCl) 0.s) were constrained by fixing them at the values obtained in Section 3 (Table 3-7).53 12.5742 0. with ∆fH°298(NaFePO4. With this restriction.64 21.46 19.14 21.s) fixed.6247 0.s) and Cp.47± 0.5633 0.39 11.

s) varied and Cp.46 kcal mol-1.48e+6 a -1. The objective of Model II is to determine Gibbs energy data for the solid that will allow a description of the solubility of maricite from 200 to 300°C.s) and C°p.s) were retained. The same approach has been followed as that in Section 4. 5-10 .52e+6 -1.s) fixed.s) was relaxed.48 kcal mol-1 and ∆fG°298(NaFePO4. ∆fH°298(maricite. (b) Model II. using the Lindsay activity coefficient model. with ∆fH°298(NaFePO4. The values from Model II have been used in the solubility calculations with MULTEQ. in which the constraint that the fit must be consistent with the experimental value of ∆fH°298(NaFePO4.s) varied and C°p.76 ± 1.T°(NaFePO4.50e+6 -1. is plotted in Figure 5-3. Again it is noted that these standard Gibbs energies apparently contain errors that compensate for errors in the activity coefficient model.s ) = -341.46e+6 b ∆aG0(Maricite) / J mol-1 -1. but again the experimental values for Cp. The least squares fit of Eqn.54e+6 150 200 250 temperature / oC 300 350 Figure 5-2 Experimental data for the Gibbs energy of formation of maricite (∆aG°) (a) Model I. 5-10 to these data.T(maricite. which have been included in Table 5-7.Solubility and Thermodynamic Model for Maricite -1.15 ± 2.s) fixed.s) fixed.44e+6 -1. ∆fH°298(maricite.T(maricite.T°(NaFePO4. The fit yields the results ∆fH°298(NaFePO4.s) = -362.

experimental. open symbols. (b) phosphate and (c) hydroxide molalities of solutions in equilibrium with maricite and magnetite: solid symbols.Solubility and Thermodynamic Model for Maricite Figure 5-3 (a) sodium. 5-11 . calculated from Model II.

mol-1 -375. using the original initial compositions as input.46 5.7 I II -347. The agreement is better than that for SIHP because the stoichiometry of the solid is fixed. Figure 5-3 shows the results of “hideout” experiments calculated from Model II using the initial conditions listed in Table 5-1. The initial hydrogen molality was estimated from the initial partial pressure.66 -341.5 Comparison with Experimental Solubilities 5. total phosphate.6). 5. The relative errors are plotted in Figure 5-4.62 -362.5.76 ± 1.1 Maricite + Magnetite + Hydrogen As was the case for SIHP. along with the experimental molalities for Na+(aq). while the measurements on SIHP used Fe2O3 . and adjusted if necessary to yield a final molality near the experimental equilibrium value.0 ± 0.Solubility and Thermodynamic Model for Maricite Table 5-7 Standard state properties of maricite at 25°C and 1bar.K-1 32. Model ∆fGo / kcal. 5-12 . Aqueous solutions in equilibrium with the reaction product mixture [Maricite + Magnetite + SIHP] are restricted by the Gibbs phase rule so that the hydrogen partial pressure and Na/PO4 ratio are fixed by the temperature and phosphate molality (See Section 5.67 ± 0. It is important to verify that the results are consistent with the thermodynamic data for Fe3O4. the accuracy of Model II for maricite was confirmed by using it to predict the compositions of the equilibrated solutions from the pressure vessel experiments as listed in Table 5-4.47 ± 0.5.15 ± 2. and the results agree to within ± 30% for all the solutions studied.mol-1.mol-1 ∆fHo /kcal. in the SUPCRT92 database Three experiments were carried out in which magnetite was reacted with aqueous sodium phosphate to form SIHP.48 So /cal.4 58. and OH-(aq) respectively. Fe2O3 and H2.2 Maricite + Magnetite + SIHP The measurements on maricite used Fe3O4/ H2 as an iron oxide buffer. under conditions which were chosen so that the hydrogen liberated as a reaction product was sufficient to also form maricite through reaction 5-1.2 ± 6.

the reactor was not charged with hydrogen. After 4-5 days 20 .30 ml of liquid phase were sampled. to allow the formation of SIHP as a reaction product without causing severe changes in the Na/PO4 ratio of the aqueous phase.Solubility and Thermodynamic Model for Maricite Figure 5-4 Relative error of solubilities maricite-magnetite-hydrogen system calculated from Model II: 100 (mexp . During the third experimental run. Three experimental runs were carried out at two different temperatures near 250°C and a fourth set of runs was carried out 320°C.15. The initial conditions required to form an equilibrium mixture with the three reaction products were identified by calculations with Model II. This addition of hydrogen shifted the equilibrium 5-13 .626 mol kg-1. the reaction vessel was charged with ∼3. The only hydrogen in the system was formed from formation of SIHP from magnetite by reaction: 2Fe3O4(s) + 26Na+(aq) + 12HPO42-(aq) + 2OH-(aq) → ← 6Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 4H2O(l) + H2(aq) (5-11) All runs started with aqueous Na/PO4 = 2. using the experimental methodology described in Section 2. The initial concentration of phosphate in the solution was 0.5 bar additional partial pressure of hydrogen using the procedure described in Section 2.mcalc)/mexp. at 265°C. In the first two runs at 255 and 265°C. The partial pressure of hydrogen formed was too small (< 10 bar) to constitute a safety hazard. after withdrawing a sample of the liquid phase.

2 2.3 2.0 2. SIHP or magnetite.1756 0.0 111.6 40.0789 0.0074 0.0170 0.0 2.0461 0. The experimental data for the molalities of sodium and phosphate in the equilibrated solutions are listed in Table 5-8.Maricite 18-1 18-2 19-1 19-2 20-1 20-2 112 184 112 232 93 261 265 265 255 255 265 265 48. Sample # Sampling Time (h) t °C ptotal bar m(Na ) (mol kg ) -1 + m(HPO4 ) (mol kg ) -1 2- m(OH ) (mol kg ) -1 - Na/P In Liquid Na/P In Solid Equilibrium Fe3O4 . The results of thermodynamic treatment with Model II are listed in Table 5-9.7 0.1672 0.0057 0.0 2.SIHP .0 2.phase mixtures of reaction products. The results at 320°C show similar agreement.2 111.0162 0.1080 0.1761 0.0357 0.0860 0.8 2. The powder patterns of the sample indicate the presence of minor amounts of magnetite and maricite and a major amount of SIHP in the solid phase. The calculated sodium and phosphate molalities for the maricite-magnetite-SIHP system near 250°C are too low by a factor of three or less.4 2. The presence of these compounds as an intimate mixture with three distinct phases was taken as confirmation that the samples had been taken while the system had been under equilibrium conditions.9 2.0199 0.0248 0.0793 0. The hardness of the new formation was considerably higher than of the maricite.0 Equilibrium Fe3O4 . however a hard cake of black-red solid deposit was observed to have formed on the bottom of the reaction vessel.0156 0.Maricite 21-1 21-2 21-3 21-4 288 333 492 573 320 320 320 320 110.0 2.0268 0.0 2. XRD analysis of the sample from the trap and from the bulk of the solid phase showed only the presence of magnetite in the solid phase.1 49.0239 0.1918 0.2 2.0716 0.0 2.2 110.9 2.3 2.1. along with those for the maricite-magnetite-hydrogen system which were discussed in Section 5.5. although the experimental data are much more scattered.5 49.3 41.3 2.0 5-14 .0101 0.0087 0.0121 0.SIHP .0115 0.0183 0.0065 0.0049 2.9 0. Table 5-8 Solubility corresponding to 3 .Solubility and Thermodynamic Model for Maricite toward the formation of maricite but left the system at invariant point conditions.9 49.6 2.0 2.0553 0.0157 2.1261 0.

1330 0.0282 0.0363 0.0444 0.kg 0.0553 0.0039 m(OH ) -1 /mol.1080 0.kg 0.0170 0.0461 0.1422 0.0121 0.0288 0.0095 0.kg 0.0386 0.1151 0.1672 0.0399 0.0162 + * Multeq simulations m(OH ) -1 /mol.0789 0.0753 0.kg 0.0270 - m(H2) -1 /mol.0753 0.1756 0.0385 + Multeq simulations a(H2) 0.kg 0.0716 0.0183 0.1042 0.0357 0.1576 Maricite+ Magnetite + SIHP Experimental results t /° C 255 255 265 265 265 320 320 run # 19-1 19-2 18-1 18-2 20-2 21-3 21-4 m(Na ) -1 /mol.0352 0.3 10 2.0353 0.3 10 8.0239 0.0026 0.kg 0.1155 0.1042 0.2829 0.0391 - m(H2) -1 /mol kg -4 8.Solubility and Thermodynamic Model for Maricite Table 5-9 Comparison between the experimental solubility of maricite and the MULTEQ simulation results Maricite + Magnetite + Hydrogen Experimental results t /° C 217 237 257 280 run # 7-2 7-8 12-3 14-3 m(Na ) -1 /mol.0306 0.1761 0.0475 0.1135 0.1330 0.1135 0.3 10 2.0442 0.0049 - m(PO4) -1 /mol.0391 0.3 10 2.0057 m(Na ) -1 /mol.4174 0.0313 0.kg 0.kg 0.0444 0.kg 0.1185 0.0407 0.kg 0.kg 0.0518 0.0444 + m(PO4) -1 /mol.0026 m(OH ) -1 /mol.2829 0.3 10 -4 -3 -3 -3 0.033 0.1422 0.0309 - m(PO4) -1 /mol.1135 0.0029 m(OH ) -1 /mol.kg 0.0157 0.1261 0.0793 0.033 * p(H2) < 10 bars 5-15 .0327 + m(PO4) -1 /mol.4174 0.0318 0.kg 0.2829 0.0115 0.0118 0.1058 0.1556 m(Na ) -1 /mol.0348 0.0753 0.0156 0.

log(Kp.3 log(m(HPO42-)) .3 log(m(Na+)) .T) .log(γ(H2(aq))) Magnetite Oxidation to SIHP 2Fe3O4(s) + 26Na+(aq) + 12HPO42-(aq) + 2OH-(aq) → ← 6Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 4H2O(l) + H2(aq) log (m(H2)) = 2 log(m(OH.6.)) . aq) ≈ 1 ): Magnetite Reduction to Maricite Fe3O4(s) + 3 Na+(aq) + 3 HPO42-(aq) + H2(aq) → ← 3 NaFePO4(s) + 3 OH (aq) + H2O(l) log (m(H2)) = 3 log(m(OH.1 Magnetite Redox Equilibria with Aqueous Sodium Phosphate in High Temperature Water The derivation of the two Gibbs energy models for maricite completes the determination of the themodynamic constants needed to model the major known ironphosphate hideout reactions encountered in boilers operating under various forms of sodium phosphate chemistry control.T) + 76 log(γ±(NaCl)) .6 Discussion 5.12 log(γ±(NaCl)) . expressed as molality of dissolved hydrogen (γ(H2.)) + log(a(H2O)) .log(γ(H2(aq))) SIHP Reduction to Maricite 6Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 2H2O(l) + 3H2(aq) → ← + 26NaFePO4(s) + 20Na (aq) + 6HPO4 (aq) + 8OH-(aq) (5-12) (5-13) (5-11) (5-14) (5-15) 5-16 .Solubility and Thermodynamic Model for Maricite 5. The entire data set is tabulated together in Appendix B. The equilibrium constant equations for the reactions of magnetite with aqueous sodium phosphate to form maricite and other hideout reaction products yield the following expressions for the redox potential associated with each reaction.4 log(a(H2O)) + 26 log(m(Na+)) + 12 log(m(HPO42-)) + log(Kp.

2 log(a(H2O)) + 20 log(m(Na+)) + 6 log(m(HPO42-)) . (ii) 5.log(Kp.)) .6. The hydrogen partial 5-17 .)) + log(a(H2O)) .log(a(H2O)) .4 log(γ±(NaCl)) .2 log(m(HPO42-)) . 5-12 to 5-21 are temperature and hydrogen molality.log(Kp.EPRI Licensed Material Solubility and Thermodynamic Model for Maricite log (m(H2)) = {8 log(m(OH. can be conveniently described by fixing m(Na)Total and m(PO4)Total . m(H2) .2 p(H2) . This has two important implications: (i) The redox chemistry of magnetite during hideout is controlled by the molalities of the dissolved sodium phosphate species. Tremaine et al.2 log(m(Na+)) . not the much lower molalities of dissolved oxygen or residual redox buffers in the boiler water Chemical equilibrium models for describing hideout are extremely sensitive to uncertainties in the activity coefficient models used to describe speciation.3 log(γ(H2(aq)))}/3 Magnetite Oxidation to Hematite 2Fe3O4(s) + H2O(l) → 3Fe2O3(s) + H2(aq) ← log (m(H2)) = log(K) .log(γ(H2)) Hematite Reduction to Maricite Fe2O3(s) + 2Na+(aq) + 2HPO42-(aq) + H2(aq) → 2NaFePO4(s) + 2OH-(aq) + H2O(l) ← log (m(H2)) = {2 log(m(OH. so that the only variables in Eqns.log(γ(H2(aq))} SIHP Formation from Hematite 3Fe2O3(s) + 26Na+(aq) + 12HPO42-(aq) + 2OH-(aq) → ← 6Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 5H2O(l) (5-16) (5-17) (5-18) (5-19) (5-20) (5-21) In earlier work.T) . (1996) noted that the most striking feature of these redox equilibria is the very large exponent on m(Na+) and m(HPO42-) in the expressions for p(H2) for reactions involving SIHP.T Diagram The implications of the thermodynamic equilibrium constant presented above.T) + 52 log(γ±(NaCl)) . and to a much lesser extent maricite.

Solubility and Thermodynamic Model for Maricite

pressure, p(H2) can then be calculated from Eqns. A-30 and A-35. The resulting plots of p(H2) vs. T show the equilibrium phase boundaries of the stable solid reaction products existing in the system Fe3O4(s) - Na2HPO4(aq) - H2O at different redox conditions and temperatures. Such stability diagrams can be used to identify the hideout reactions that occur when magnetite is exposed to different conditions of temperature or hydrogen pressures while in contact with a given sodium phosphate solution. A stability diagram for m(Na+) = 0.1mol kg-1 at the sodium-phosphate ratio m(Na)Total/m(PO4)Total = 2.5 is presented as Figure 5-5. The redox potential of the system is plotted as log p(H2,g), the logarithm of the partial pressure of hydrogen in the vapour phase in the reaction vessel. Open areas on the phase diagram represent conditions where only one solid phase exists in equilibrium with the liquid and vapour phases; lines correspond to two coexisting solid phases in equilibrium with liquid and vapour phases; and the intersection of three lines occurs at points where three solid phases are in equilibrium with the liquid and vapour phases.

5-18

EPRI Licensed Material Solubility and Thermodynamic Model for Maricite

3

2 Maricite 1
c f

log(P(H 2)) / bar

0
2

-1 Fe3O4 -2
a

d

SIHP
3
b

-3

Fe2O3

1
e

-4 200

225

250

275 t/ C
o

300

325

350

Figure 5-5 An approximate stability diagram for the iron/sodium/phosphate/water system, calculated with m(Na+,aq) = 0.1 mol.kg-1, Na/PO4 = 2.5.

Meaningful stability diagrams are not easily calculated for these systems, because the activity coefficient and speciation effects associated with Reactions 5-11 to 5-21 are so large that a chemical equilibrium model must be used. MULTEQ is not configured to carry out such calculations, so that iterative hand calculations were required for this work. The temperature dependance of p(H2) in Figure 5-5 was calculated from the equilibrium constants in Appendix B. The calculations are approximately consistent with Model II, although there are minor differences arising because an early version of the model was used. The phase equilibria in the sodium/iron/phosphate/water system are discussed below, with the aid of the stability diagram. With reference to Figure 5-5, lines ab and cd represent the equilibrium lines for the transformations from Fe2O3 to Fe3O4, and from Fe3O4 to maricite with increasing hydrogen partial pressure, according to Eqns. 5-18 and 5-13. Line eb is the phase 5-19

Solubility and Thermodynamic Model for Maricite

boundary between Fe2O3 and SIHP, which is independent of hydrogen partial pressure since both are iron(III) compounds. Lines bd and df represent the Fe3O4/SIHP and SIHP/maricite equilibria, Reactions 5-14 and 5-16, respectively. The p(H2) - T diagram contains two points, at b and d, where three solid phases coexist. Point d corresponds to the case studied above, where the three solid phases magnetite + maricite + SIHP are in equilibrium with the vapour and liquid phases. Point b corresponds to the magnetite + hematite + SIHP equilibrium mixture of solids. At these two points the system consists of six formal components, traditionally designated as: FeO, Fe2O3 , P2O5, H2, Na2O, and H2O, and five phases. From the Gibbs phase rule, there are three degrees of freedom (f = components - phases + 2 = 6 - 5 + 2 = 3) so that only three of the five variables (temperature, pressure, hydrogen molality, sodium molality and phosphate molality) can be varied independently. Pressure is determined by the steam saturation pressure of the solution, and the sodium and phosphate molalities on the p(H2) - T diagram are fixed at their pre-selected values. Thus, if three solid hideout reaction products exist at equilibrium, then the hydrogen molality and temperature are also fixed. Lines 1, 2 and 3 on the figure indicate the experimental paths similar to those used to form (1) SIHP from hematite, (2) maricite from magnetite, and (3) the maricite/SIHP/magnetite mixture from magnetite, in the experimental measurements. A true invariant point, in which four solid phases coexist, occurs at one fixed molality of sodium and phosphate for each temperature. The molalities of sodium and phophate are invariant under these conditions at steam saturation, if the temperature and partial pressure of hydrogen are fixed because, from Gibbs phase rule (f = components - phases + 2 = 6 - 6 + 2 = 2), temperature and hydrogen molality are the only two degrees of freedom. Figure 5-6 is a schematic diagram of the changes in the phase behavior as the sodium phosphate ratio is varied over a wide range at constant phosphate molality. At low Na/PO4 ratios, magnetite can be transformed to hematite and maricite by raising the temperature.

5-20

EPRI Licensed Material Solubility and Thermodynamic Model for Maricite

Figure 5-6 An approximate stability diagram for the iron/sodium/phosphate/water system, + -1 calculated with m(Na ,aq)=0.1 mol.kg at low Na/PO4 ratios: (a) Na/PO4 = 2.0 and (b) Na/PO4 = 2.2

5-21

Solubility and Thermodynamic Model for Maricite

Figures 5-5 and 5-6 are examples of the stability diagrams that can be constructed from the data in Appendix B, to understand the effects of redox conditions arising from hideout processes. The database in Appendix B is sufficient to calculate quantitative phase diagrams, but the MULTEQ software is not configured for these calculations and the development of the parameters and data for the necessary calculations with other software is beyond the scope of the present study. The implications for boiler chemistry control are discussed in Section 6.

5-22

using Model II in conjunction with MULTEQ. usually only 10 to 15 µm thick.1 The Stability of Magnetite Films Magnetite is formed in boilers by the oxidation of iron in neutral or alkaline water under reducing or only slightly oxidizing conditions. 6-1 .08 mol kg-1 phosphate solution at Na/PO4 ratios ranging from 1. The calculations were carried out at a temperature of 275°C.25 mol kg-1 of Fe3O4 was allowed to react with a 0. Often the protective inner layer is covered by loose. The equilibrium constants determined in this report for SIHP and maricite. Three questions must be addressed: (i) What is the nature of the hideout reaction products that form under various sodium/phosphate ratios? What is the mechanism for the severe corrosion damage that occurs in some stations operating under congruent phosphate treatment? What reactions control the pH and redox chemistry under normal operating conditions? (ii) (iii) A set of calculations was performed in which 0. It grows as a rugged coherent film on carbon steel. The thermodynamic data in Model II can be used to evaluate the stability of magnetite under hideout conditions. which protects steel surfaces against corrosion. and reported in Appendix B.EPRI Licensed Material 6 MAGNETITE STABILITY UNDER HIDEOUT CONDITIONS AND IMPLICATIONS FOR POWER STATION CHEMISTRY CONTROL STRATEGIES 6. This represents a hideout condition in which the protective film on ∼ 1 m2 of carbon steel is exposed to boiler water that has been concentrated by a factor of ∼ 4000 from the normal bulk value of ∼ 10-5 mol kg-1 ( 3 ppm PO4).0 to 100. to minimize errors in the database which are smallest at the midrange region of the data. non-protective deposits which have been deposited from solution by precipitation-and-growth or particle transport mechanisms.

08 mol.kg Fe3O4 reacts -1 with 0.8(H3O)0. Figure 6-1 -1 Calculated inventories of hideout reaction products when 0.2PO4.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies do not require data for Fe2+(aq) because the solids were in equilibrium with magnetite or hematite. Because the MULTEQ database for Fe2+(aq) is not consistent with that used in SUPCRT92. The input format used by MULTEQ requires equilibria expressed in terms of Fe2+(aq). 6-2 . “NaP28S” is the sodium phosphate phase Na2.kg phosphate solution at various (Na/PO4)initial ratios (from model II). it was necessary to introduce new values for ∆aG°T(Fe2+. The results of these calculations are plotted in Figures 6-1 to 6-6.aq) that yield equilibrium constants consistent with the solubility product of magnetite in MULTEQ.25 mol.

Figure 6-3 The inventories of aqueous phosphate consumed as reaction products in the calculation plotted in Figure 6-1. 6-3 .EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies Figure 6-2 The percentage of Fe3O4 consumed as iron-containing reaction products from the calculation plotted in Figure 6-1.

6-4 .5 (Na/PO 4)solid 2.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies 3.0 2.0 1.0 1 2 3 4 5 10 (Na/PO4)initial 50 100 Figure 6-4 The sodium phosphate ratio in the solid hideout product from the calculation plotted in Figure 6-1.5 1.

0 12.0 5.0 4.0 9.0 (Na/PO 4)initial 8.0 pH 7.0 0.0 (b) pH and -(log Kw) /2 vs (Na/PO 4)initial 10.0 10.0 6.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies 100 (a) (Na/PO4)final.0 Figure 6-5 Aqueous (Na/PO4) ratio and equilibrium pH from the calculation plotted in Figure 6-1.0 pH -(log Kw)/2 2. 6-5 .0 8.0 4.liquid 10 5 2.0 6.5 1 1 2 3 4 5 6 7 8 9 10 (Na/PO 4)initial 11. liquid vs (Na/PO 4)initial 50 25 (Na/PO4)final.

Na3-2x FeIIxPO4.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies 10-2 10-3 10-4 m H2 10-5 10-6 10-7 1 2 3 4 5 10 (Na/PO4)initial Figure 6-6 The redox potential corresponding to the calculation from Figure 6-1. At low ratios. The pure sodium phosphate phase Na2. plotted as hydrogen molality m(H2). This is unexpected because it has been thought that Na2. (1992. Na/PO4 > 40. except that no experimental evidence for the formation of the non-stoichiometric cubic solid solution.2 ≤ Na/PO4 ≤ 25 are consistent with those observed by Tremaine et al. hematite appears along with maricite as a reaction product and. Figures 6-2 and 6-3 show the percentage of the initial magnetite and aqueous phosphate consumed by hideout reactions. The results predicted for initial ratios 2. summarized in Figure 1-5. 50 100 Figure 6-1 shows the number of moles of each hideout reaction product formed as a function of the sodium/phosphate ratio in the initial solution. SIHP is the major iron hideout reaction product at higher Na/PO4 ratios while maricite dominates at low Na/PO4 ratios. at very low ratios the amount formed is substantial. This has profound implications for phosphate boiler-water chemistry control. Na/PO4 ≤ 2.8(H3O)0.2PO4 was 6-6 .0.2PO4 only appears at very high ratios.8(H3O)0. There are four distinct regions in these diagrams. has been found in the present work and no data for its formation were included in the models. 1993) at 360°C. As would be expected from the stoichiometry and the activity diagrams in Section 5.

. 1975.8(H3O)0.5).8(H3O)0.. Tubes in some stations operated under these conditions have been observed to undergo very severe attack. the principal phosphate species is H2PO4-(aq) so that the predominant hideout reaction is: Fe3O4(s) + 3 Na+(aq) + 3 H2PO4-(aq) + H2(aq) → 3 NaFePO4(s) + 4 H2O ← (6-1) 6-7 . 1994. equilibrium pH and redox conditions. During the first cycle through the boiler. yield alkaline reducing conditions. and there has not been an attempt to verify the model for Na2. This is the first time a mechanism for the corrosive phosphate attack has been identified that is consistent with field observations. 1977. the protective magnetite films under deposits or steam bubbles on the boiler tubes may be exposed to solutions with Na/PO4 ≤ 2. the exact ratio at which Na2. 1996).2 A Mechanism for Severe Corrosion Damage at Low Na/PO4 Ratios The plots in Figures 6-2 and 6-3 suggest that very severe attack on magnetite films will occur when they are exposed to solutions with Na/PO4 ≤ 2. At Na/PO4 = 1. Dooley and Paterson. It has been common practice. This is in sharp contrast with the reaction of magnetite to form hematite and maricite at Na/PO4 ≤ 2. Figures 6-4..2. which is accompanied by a sharp drop in both the pH and concentration of dissolved hydrogen. The characteristic damage pattern in these attacks is typically in the form of deep gouges containing a mixture of maricite and hematite (Dooley and McNaughton. At these low sodium/phosphate ratios.2PO4 used in MULTEQ (Baes and Lindsay. 1955). The data in Figures 6-1 to 6-3 suggest that this kind of attack occurs because the local conditions exceed the solubility threshold for the formation of maricite so that extensive areas of protective magnetite are converted to non-protective hematite. Economy et al.0. expressed as p(H2). Dooley et al.6 by adding relatively concentrated solutions of monosodium phosphate and/or disodium phosphate to the boiler water.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies the principal reaction product controlling hideout chemistry under normal conditions (Broadbent et al. As a result. Over 40% of the aqueous phosphate has been consumed. 6. The hideout reactions at Na/PO4 > 2. Errors in Model II are greater at high sodium/phosphate ratios (Section 4. Ravich and Scherbakova. in some stations operating under congruent phosphate treatment. with another 5% reacted to form maricite. At Na/PO4 = 1.5. 1996. before the solutions are diluted and thoroughly mixed. in which SIHP is formed. 6-5 and 6-6 plot the Na/PO4 ratio.e. over 10% of the magnetite has reacted to form hematite. over 20% of the magnetite has been oxidized to hematite by the formation of maricite.0 under hideout conditions in high temperature water.2PO4 replaces SIHP as the major hideout reaction product is uncertain. 1994).0. that the corrosion is thermodynamic in origin.0. corresponding to the results in Figure 6-1. i. to maintain ratios of Na/PO4 below 2.

These latter phases are in the MULTEQ database.total] < 10 ppm.8.8(H3O)0. 6. Furthermore Na2. 1994) which recommend use of the EPT method of phosphate chemistry control and an extension (“Phosphate Treatment”. The results in Figures 6-1 to 6-5 yield new insights as to the nature of the hideout reactions encountered during normal operation under the EPT or PT treatments. 1977. 2.2 < Na/PO4 < 2. Recently EPRI released new guidelines (Dooley et al. However.. These may cause further excursions into acidic pH conditions and other forms of damage.8 the major reaction product is SIHP which forms according to the reaction 2Fe3O4(s) + 26Na+(aq) + 12HPO42-(aq) + 2OH-(aq) → ← 6Na3Fe(PO4)2·(Na4/3H2/3O)(s) + 4H2O + H2 (6-3) It is very apparent from laboratory experience.3 Hideout Reactions at Moderate to High Na/PO4 Ratios The “Equilibrium Phosphate Treatment” (EPT) procedure used successfully by Ontario Hydro and many Canadian utilities is based on lower phosphate molalities ( < 3ppm) and higher Na/PO4 ratios (Na/PO4 > 2.2PO4 was only observed to form from solutions at very high Na/PO4 ratios. It appears that the water chemistry is largely controlled by the iron reaction products. As noted above..EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies It is the consumption of hydrogen by Reaction 6-1 that drives the conversion of magnetite to hematite: 2Fe3O4(s) + H2O → 3Fe2O3(s) + H2(aq) ← (6-2) Although the degree of attack associated with the formation of hematite from the phosphate hideout reaction itself is more than enough to account for the field observations. it is likely that the onset of the more oxidizing conditions and buffered neutral pH that accompany the formation of hematite and maricite will initiate other forms of corrosive attack on the exposed surfaces of the underlying carbon steel in the tube wall.. and that Na2HPO4(s) or the phase-separated liquids. it had been thought that Na2. might form at low sodium/phosphate ratios.6). 1975).2PO4 was the principal reaction product controlling hideout chemistry under normal conditions (Broadbent et al. PT) to include phosphate concentrations as high as 10 ppm . shown in Figure 1-3. Under EPT and PT conditions at Na/PO4 > 2. and that it can attack magnetite.8(H3O)0. that Reaction 6-3 can be rapid and reversible.8) than those used in the Congruent Phosphate Treatment ( 3 < [PO4. the percentage of magnetite reacted under EPT conditions in the calculations shown in 6-8 . but have not been observed in any of the calculations between 200 and 325°C when maricite or SIHP were present. Economy et al. in this work and elsewhere. but always at Na/PO4 > 2.

1994) suggest that. because the phosphate concentrations in the bulk water are higher. If the protective film does react. Figure 6-8 is very approximate and is intended to illustrate the pattern of behavior.2 leads to the formation of hydrogen (Figure 6-8c). It has hitherto been impossible to assess the extent of SIHP formation in operating stations. thereby oxidizing it to form hematite. PT conditions are of more concern than EPT. of the local conditions under which SIHP and maricite will form. the formation of maricite from solutions with Na/PO4 ≤ 2. much of the reaction may take place with loose surface deposits of magnetite rather with the protective magnetite film. rather than quantitative results. it is highly likely that local conditions would favour the formation of adherent protective films of additional magnetite through oxidation of the underlying steel when the phosphate concentration falls below the threshold required to sustain Reaction 6. in conjunction with laboratory experiments to confirm the generality of these findings. because SIHP redissolves to form aqueous phosphate and hematite during cool-down so that it is rarely recovered. The results presented above have demonstrated that the evaporation or “dry out” of boiler water with different sodium/phosphate ratios can lead to very different reaction products and redox conditions. the hideout formation of SIHP at Na/PO4 > 3.0 preferently removes iron(II) from the magnetite.0 the equilibrium hydrogen pressure is substantial (Figure 6-6) and quite strongly reducing conditions are established. and the paths of the hideout reactions on the stability diagrams are illustrated in Figure 6-8. the presence of phosphate would be much preferred over that encountered when only NaOH is used to control the bulk pH. Moreover.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies Figure 6-2 is much less than that taking place at lower sodium phosphate ratios where hematite is formed. Since magnetite is the most reduced iron oxide under boiler conditions. should be carried out. If so. because both the pH and redox potential are buffered by the formation of SIHP as shown in Figures 6-5 and 6-6. the formation of SIHP from solutions with high sodium/phosphate ratios. reducing conditions. under EPT and PT conditions. the damage or tube thinning may be modest relative to corrosion processes that arise from high local concentrations of caustic during hideout when phosphate is not used. As shown in Figure 6-8a. in regard to the effect of Reaction 6-3 on long term boiler tube integrety. Na/PO4 > 2. At Na/PO4 > 3. The MULTEQ calculations with Model II are believed to be accurate within the uncertainties discussed in Sections 4 and 5. Figure 6-7 is intended to illustrate rapid and extensive damage to the protective magnetite film that accompanies Reactions 6-1 and 6-2 at low sodium/phosphate ratios.0 by Reaction 6-3 yields alkaline. for the first time. field observations (Dooley and Paterson. 6-9 . Furthermore. Much more extensive calculations. A schematic diagram of the processes predicted by Model II is shown in Figure 6-7. Although the formation of SIHP results from reaction with magnetite. The results of this research allow predictions.3.2 the four solids coexist (Figure 6-8b) and buffer the redox potential at a much less reducing condition. At Na/PO4 = 2. like those in Figures 6-1 to 6-6.

the results are consistent with field experience and much of the known laboratory work on iron phosphate interactions under hideout conditions. N a/PO 4 (aq) < 2.0 N aF e II P O 4 S IH P F e II F e 2 IIIO 4 3.0 # N a/PO 4 (aq) # 3.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies Nevertheless. II III 6-10 .0 H+ N aF e P O 4 II H 2PO 4Fe2 O 3 III F e II F e 2 IIIO 4 2.0 < N a/P O 4 (aq) N a+ H 2 (aq) OHS IH P Fe Fe2 O 4 Figure 6-7 A schematic diagram of the reaction mechanism of Fe3O4 at 275°C corresponding to the calculation plotted in Figure 6-1.

showing the hideout reaction paths during heating: (a) Na/PO4 = 2. and (c) Na/PO4 = 3.5.2 b 3 Na/PO4 = 3.1 mol/kg-1. calculated with m(Na+. (b) Na/PO4 = 2.EPRI Licensed Material Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies a 3 2 1 0 log(P(H 2)) / bar -1 -2 -3 SIHP -4 Fe2O3 -5 -6 200 -5 -6 200 -4 Fe2O3 Maricite log(P(H 2)) / bar Na/PO4 = 2.0.2. 6-11 .5 2 Maricite c 1 0 -1 Fe3O4 -2 -3 SIHP -2 Maricite log(P(H 2)) / bar 0 Fe3O4 -1 SIHP Fe3O4 -3 Fe2O3 225 250 275 t/ C o 300 325 350 225 250 275 t/ C o 300 325 350 -4 200 225 250 275 t/ C o 300 325 350 Figure 6-8 Approximate stability diagram for the iron/sodium/phosphate/water system.0 2 1 3 Na/PO4 = 2.aq) = 0.

along with the formation of neutral. (ii) (iii) (iv) (v) The calculations reported here are a very preliminary. The results show for the first time that hideout from boiler water at low sodium/phosphate ratios. in conjunction with small scale coupon tests and larger scale loop experiments to examine site-specific hideout conditions. not the much lower molalities of dissolved oxygen or residual redox buffers in the boiler water The thermodynamic constants for SIHP and maricite have been incorporated into the chemical equilibrium program MULTEQ and used to assess the nature of the hideout reactions with magnetite that occur at different sodium/phosphate ratios. This is probably the mechanism for the severe corrosion of carbon steel boiler tubes in some stations operated under congruent phosphate chemistry treatment. The redox chemistry of magnetite during hideout is controlled by the molalities of the dissolved sodium phosphate species. These may yield beneficial effects which inhibit corrosion and thus compensate for modest reductions in pressure tube thickness if the hideout reaction takes place on the passivating film rather than on loose magnetite deposits. oxidizing conditions in the local aqueous phase. because of the stoichiometry of sodium in Reaction 6-1. and ammonia on these iron phosphate interactions. the formation of SIHP and hydrogen from the oxidation of magnetite by sodium phosphate may be the major reaction controlling water chemistry under hideout conditions. causes extensive attack of magnetite to form hematite and maricite. and to assess the effects of other dissolved salts. The reaction yields local conditions which are reducing and alkaline. Model II will not extrapolate 6-12 . The chemical equilibrium models for describing hideout are extremely sensitive to uncertainties in the activity coefficient models used to describe speciation. and the earlier work of Quinlan (1996).4 Conclusions and Recommendations The results of this work. Much more detailed work should be done. At higher Na/PO4 ratios. Na/PO4 ≤ 2. As a result.0.Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies 6. exploratory study of local hideout effects arising from iron-phosphate interactions using Model II. may be summarized as follows: (i) Extensive laboratory measurements have been made by pressure vessel techniques and calorimetry to determine thermodynamic constants for the phosphate hideout reaction products SIHP and maricite. organic species.

1991. and a treatment for the non stoichiometry of the solids using established techniques (Pitzer. 6-13 . These extensions to the model should be carried out. Baes and Lindsay. 1994). The database is now sufficient to develop better activity coefficient models. nor will it give accurate results at high Na/PO4 ratios because the non-stoichiometry of SIHP is not included.Magnetite Stability under Hideout Conditions and Implications for Power Station Chemistry Control Strategies accurately to high pressure boiler conditions (325 to 365°C).

.

and Japas M.R. Ref. (1986) The thermodynamics of solvation of ions.EPRI Licensed Material 7 REFERENCES Abraham M.I. Alexander J. Thermodynamic properties of NaCl(aq). Corti H. Inorg. (1989) MULTEQ: Equilibrium of an electrolyte solution with vapor-liquid partitioning and precipitation.. 3255-3274. EPRI Report NP-5561CCM. Virginia R. and Luu L. J. Sopocy D. 1720-1723.. Jonas O. Part 1. NACE International. Aschoff A. I 82.H. 7-1 . Vol I. Staehle W. (1992) Thermodynamic properties of the NaCl + H2O system II. Chem. and Lindsay W. editors. Proceedings of Conference on Improving the Understanding and Control of Corrosion on the Secondary Side of Steam Generators. Phys.(1996) Modeling the formation of variable-composition liquid or solid phases in MULTEQ. Lee Y. Baes C. Borovaya F.(1994) Distribution of solutes between coexisting steam and water.W.T. Fernandez Prini R. and Ravich M. and McIlree A.A. J. Soc.The heat capacity of hydration at 298. Gorman J.. Chem.H. (1968) Thermochemical Kinetics. Data 21.M. pp 577-600.. and phase equilibria. Alvarez J. Benson S. J. 793-823. Geochimica et Cosmochimica Acta 58.L. (1984) Interim concensus guidelines on fossil cycle chemistry. Wiley.H. Chem. New York. 2789-2798. Faraday Trans. Users Manual. Russ. Archer D. and Marcus Y. (1968) Solubility of sodium carbonate and orthophosphate in aqueous solutions of sodium hydroxide at elevated temperatures.E. Houston.F. NY.R.G..W..15K .F. NaCl·2H2O(cr). EPRI Report CS 4629. 13...

and Regazzoni A. 903-906. 219-228. Theory and Practice.N. 763-768. Broadbent D. 14. Chem.. Nuclear Reactor Systems (London) pp. Chem. Blesa M.. Quinlan S.(1975) Zinc perchlorate: enthalpies of dilution with water and some enthalpies of mixing with perchloric acid.G. Water Chem. EPRI Report TR-103655.E. Boiler Tube Failures. FL. (1978) The chemistry of high temperature phosphate solutions in relation to steam generation.. (1977) Phase equilibria in aqueous sodium phosphate solutions at elevated temperatures. CEGB Research Report NW/SSD/RR/67/78.EPRI Licensed Material References Berg R. Jr. Materials 10.J. and Pocock F.. Data.... J. Chem. A. and McNaughton W. (1985) JANAF Thermochemical Tables. CODATA Recommended key values for thermodynamics 1977. E. CA.A. Sup.G. R. 7-2 . N. 7.P. Broadbent D. and Wetton E.. McDonald R. Electric Power Research Institute.. Chapter 16. J..A. (1996). (1994) Cycle chemistry guidelines for fossil plants: phosphate treatment for drum units. Frurip D. Chase M. Chem. Dooley R. Part IV Corrosion of mild steel in sodium phosphate solutions at 250°. Bridson J.A. Thermodyn. Mackenzie J. A. 5. No. EPRI Book TR 105261. Broadbent D. CRC Press. EPRI Report NP-2963. Dalton Trans. 300° and 350°C. Chem.M. Thermodynamics 10. (1994) Chemical dissolution of metal oxides. Soc. Dooley B. and Panson A.. Morando P. J.. (1983) Investigation of phosphate-sludge interactions.B. Ref.J.(1998) Synthesis and crystal structure of maricite and sodium iron(III) hydroxy phosphate. Downey J.M.M.. Palo Alto..M. and Tremaine P. Connor W. Proc. and Wetton E... Jr. 464468. 53-62. Vol 2.A. and Wetton E. Davies C. and Vanderzee C. Phys. (1978) High-temperature phosphate chemistry. BNES Conf. J. and Syverud A.. CODATA Task Group(1977).R. Boca Raton. W.1. Aschoff A.. J. Lewis G. Lewis G.

J. Water Conf. Proc. (1987) Proc. III.C. EPRI. Chem. (1994) Phosphate treatment: boiler tube failures lead to optimum treatment. (1976) Theoretical prediction of the thermodynamic properties of aqueous electrolytes at high pressures and temperatures. 12491516. aqueous 7-3 . Soc. C. Am. Chem. EPRI Conf. Water Conf. (1984) NBS/NRC Steam Tables. Am.H. and Lindsay W.S.N.J. GA..H. Proc. 87. (1957) The mechanism of formation of sodium triphosphate from orthophosphate mixtures. Delaney J. PA. Economy G. PA. Goldman S. Oelkers E. 94. 97-240.. Theoretical predictions of the thermodynamic behaviour of aqueous electrolytes at high pressures and temperatures.). and Kirkham D. Thermodynamic and Transport Properties and Computer Programs for Vapour and Liquid States of Water in SI Units. Nesbitt H.S. 278A. 79. and Bird D. Amer.. (1975) Sodium phosphate solutions at boiler conditions: Solubility.. 1476-1484. Johnson J. and Paterson S. Calculation of activity coefficient.173. 55th Int.W. Sci. Helgeson H.F.E. (1978) Summary and critique of the thermodynamic properties of rock-forming minerals. 1988. Soc. osmotic coefficients. IV. eds. and apparent molar and standard and relative partial molar properties to 600°C and 5 kb. 1-229. Gallagher J. Dooley R.M. Edwards J. and Kell G. Hemisphere Publishing. H. (Pittsburgh. Haar L. Phys. and Helgeson H. Am..) pp. 1242-1255.G. Helgeson H. Holmes H. Jr.. Equation of state for aqueous species at infinite dilution. C. J. J.H. phase equilibria and interactions with magnetite. gases.T. and Flowers G.. B. CS-5500-SR. New York .) Paper IWC-94-50. Kirkham D... and Bates R.W. Helgeson H. 281. (Pittsburgh.K. (1992) Supcrt92: A software package for calculating the standard molal thermodynamic properties of minerals. J. and Broske D.. (1972) Calculation of thermodynamic functions for ionic hydration. Esposito J.C.. (1983) Thermodynamic properties of aqueous solutions of the alkali metal chlorides to 250°C.. Chem. Panson A. and Mesmer R. Sci. 36th Int. and Herzog A.W. (Atlanta. (1981). Boiler Tube Failures in Fossil Power Plants. Liu Chia-tsun.. J. J. 276. 3647-3650.C. 161 .EPRI Licensed Material References Dooley R. Am. Sci..B.

pp.(1977) “The crystal structure of the new mineral maricite. NY. Soc. Sifner.(1968) Electrode potentials and thermodynamic data for aqueous ions copper. (1987) Water side corrosion in the water wall tubes of Hunter Unit 3. 2902-2907. New York. Soc. Chem. T. W. and Hepler L.EPRI Licensed Material References species and reactions from 1 to 5000 bar and 0 to 1000°C. Maier C.K. bicarbonate ion. (1932) An equation for the representation of high temperature heat content data. Computers and Geoscience 18(7). Amer. NaFePO 4. and Hepler L. Chem. (1990). 375-386. and Wallace G. (1982) Two-liquid-phase boundaries and critical phenomena at 275-400°C for high-temperature aqueous potassium phosphate and sodium phosphate solutions. Layton K. G. eds. cobalt and nickel.K. 72. Engineers. Am. and Donnay G. Phys. on Boiler Tube Failure in Fossil Plants (Atlanta.G.. Data 27. Chapter 7. 49. Mech. (1927) The dissociation pressures of monopotassium and monosodium orthophosphates and of dipotassium and disodium dihydrogen pyrophosates.W. 899-947. Larson J. J. Can. Lindsay W. Larson J.H. J.. Jr.. Combustion Jan. Phosphate IV.” Canadian Mineralogist 15. 60. 29-38. and Halstead S. Zeeb K. 2141-2150.J. LePage Y. G. Potential applications for steam generators. New York. 175-180. and bisulphate ion in aqueous solution. Chem. Soc. Chem. in Properties of Water and Steam M. 45-47. 341-544..M. Chemistry of steam cyle solutions: principles.L. 518-521. Marcy V. J. Hemisphere Publishing. 2ed. (1989) Computer modeling of aqueous systems in power cycles. Lindsay W. GA). in The ASME Handbook on Water Technology for Thermal Power Systems. Proc. Chem. zinc.G. 3243-3246.T... J. and 3th). Eng. EPRI Conf.. iron.F. P. and Kelley K. 7-4 . NY. Cohen. ed..(1982) Heat capacities and volumes of dissolution of phosphoric acid (1st. J. Garber H. Marshall W. Kiehl S.L. (1964) Improved basis for coordinated phosphate-pH control of boiler water. Amer. Cerutti P. Pichal and O. 54.

Economy G. and Begun G. D. Bulischeck T. Inst.B. J.. J. Jr.A.E. (1989) Raman spectroscopy of aqueous phosphate solutions at temperatures up to 450°C. 15. Duer W.L. Sektora Fiz. Khim.. Faraday Trans. Mesmer R. Marshall W. Washington. Eng. Khim. 307 .. Morey G. Solution Chem. and Baes C. 59 . F.J. theoretical. Solution Chem. Fundam.Sc. and Chetirikin P.. Ravich M.918.64. 877-889 . and Scherbakova L. 5. and applied aspects. Soc. Chem. Chem.. (1996) Thermochemistry of aqueous sodium phosphate interactions with metal oxides in high temperature water. and Silvester L. Quinlan S.L. 2 85. (1976) Thermodynamics of electrolytes. 915 . Solution Chem 3. (1991) Activity Coefficients in Electrolyte Solutions. J.I.EPRI Licensed Material References Marshall W. Electrochem. 2nd ed. 248-258. (1974) Phosphoric Acid dissociation equilibria in aqueous solutions to 300°C. Ind. Izvest.. Liu Chia-tsun. National Standard Reference Data Series NSRDS-NBS 2 (National Bureau of Standards. Nauk SSSR 26. (1976) A new two-constant equation of state. Pitzer K.J... Chem.. Chem. and Lindsay W. 5794-5797. Boca Raton. FL.W. J. 57. Yu and Robinson D. Weak Electrolytes Including H3PO4. Amer.V. (1965) Thermal Properties of Uni-Univalent Electrolytes.(1978) The enthalpies of dilution of phosphate solutions at 30EC.322. Panson A. (1975) Sodium phosphate solubility and phase relations basis for invariant point chemistry control. S. 7.. Millero F. Parker V. J.F.T. 122. Akad. 283-301.) Peng D. Obshchei Neorg. M. Shepard E. Memorial University of Newfoundland.S.. Pitzer K.. Thesis. Anal. Soc. 12.S.C.C.B. 269-278.M. 7-5 . 75. Soc. (1955) Nature of the solid phase which crystallizes from aqueous solutions of trisodium orthophosphate at high temperatures. VI. (1985) Aqueous inorganic phase equilibria at high temperatures: Some experimental. (1953) The system H2O-NaPO3 . J. 1963-1978. Pure and Appl. CRC Press.

. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5kb and 1000°C. Acta. J.F (1970). (1952) The Growing of single crystals of magnetite. 803-826. and Helgeson H.. and Helgeson H.15 K. Geochim. 191 .C. Chem. 19-98. Stumm W.(1984) Enthalpy of solution of KCl and NaCl in water at 298. (1988). New York. Effect of sodium hydroxide and sodium phosphate. Sci. (1992) Calculation of the thermodynamic properties of aqueous species at high pressures and temperatures. Schroeder W.C.. October 1996. Soc.214.E.A. Sweeton F..J. Am. Effective electrostatic radii. (1996) Boiler water alkalinity control. 88. J. and Helgeson H. J. Chem. NY.C. 7-6 . J. J. Sweeton F. (1970) Aquatic Chemistry. 20..A. Soc. III.H. Stodola J. Chem. Acidity measurements at elevated temperatures VII.H. 479-500. Berk A. Cosmochim.. 16. Dissociation of Water. Pittsburg. 6. 52. 1195-1202.F. (1974).. Oelkers E. 59.H. 288. International Water Conference. Revised equation of state for the standard partial molar properties of ions and electrolytes. Smiltens J. dissociation constants and standard partial molar properties to 1000°C and 5 kbar. (1937) Solubility of equilibria of sodium sulfate at temperatures from 150 to 350°. 3. 1783-1790. Shock E. PA . and Morgan J. Johnson J. Chem. The solubility of magnetite and the hydrolysis of ferrous ion in aqueous solutions at elevated temperatures. J. 990994. and Baes C. Solution Chem.. C.W. Thermodynamics 2. and Gabriel A.EPRI Licensed Material References Sanahuja A. and Cesari E. Proc. Chem.. Shock H. Mesmer R. Faraday Trans. L. Phys. and Baes C. Amer. J. 2009. Wiley-Interscience.C. (1988) Calculation of the thermodynamic and transport properties of aqueous species at high temperatures and pressures. Sverjensky D.L... Tanger J. Thermodyn.

Ind.Vol II. Van Wazer J. Wendrow B. 57th Int. 104 pp.. No. J. Vanderzee C.. Quinlan S. Parker V.S. and Taylor P. Paper IWC-93-35.. Chem.R. Tremaine P.. J. 44.. and King D. Inorganic Chem. Phys. L. Tremaine P... 183 pp.A.R.Vol III.A. E. Phys Chem. 25-30. 1996) Paper IWC-96-21.R. Gray L. Wiwchar B. 29472953. R&D Agreement 913G730. and Kobe K.R. and Taylor P. (1981) Phase equilibria in aqueous sodium phosphate solutions at 350°C. Proc.R and LeBlanc J. L.. Proc. Sway K. (1979) Enthalpies of dilution and relative apparent molar enthalpies of aqueous chromium (III) perchlorate.. J.A. (1958): Phosphorus and Its Compounds. 151-158. (1992) Sodium phosphate chemistry under high pressure utility drum boiler conditions. Bailey S. Data.M. Stodola J. (1993) Phosphate interactions with metal oxides under high-pressure boiler hideout conditions. Stodola J. Gray L. Schumm R.R.. (1996) Solubility and thermodynamics of sodium phosphate reaction products under hideout conditions in high-pressure boilers.. Wetton E. N. and Nuttal R.C. and Barbero J. Halow I. Eng.. 11... Power Industry Research 1. 196 pp. J. (1986) The apparent molar heat capacity of aqueous hydrochloric acid from 10-140°C. L. 415-442. J.(1980) The solubility of magnetite and the hydrolysis and oxidation of Fe2+ in water to 300°C. Interscience. Water Conference. Wagman D. Tremaine P.. and Stodola. Chem.. 11. 1439-1448. (1955) The system sodium oxide-phosphorus pentoxidewater. October. Evans W. Sup.. Thermodyn. October.. 7-7 .G. (1979) Sodium oxide-phosphorus (V) oxidewater phase diagram near 300°C: equilibrium solid phases.. Tremaine P. 54th Int. 15.G... H.. B. Can. Chem. (Pittsburg. 1-22 Tremaine P..R. Final Report Vol I. Electrical Assoc. Tremaine P.Y. 9. H.. 11. D.EPRI Licensed Material References Taylor P. Churney K. (1982) The NBS Tables of Chemical Thermodynamic Properties.2. Ref.G. and Bailey M. Water Conference (Pittsburg. Wiwchar B. M. Solution Chem. 1993). Bridson J.

. Proc. in “Physical Chemistry of Aqueous Systems: Meeting the Needs of Industry”. Sixth International Symposium on Environmental Degradation of Materials in Nuclear Power Systems . Begell House.). (1995) Standard partial molar heat capacities and volumes of aqueous divalent and trivalent ions from measurements near 25°C.J. (1997) The Thermodynamics of aqueous electrolytes and hydrogen bonded nonelectrolytes over a wide range of temperature and pressure: The aqueous trivalent lanthanide cations and the methanol-water system.E. and Tremaine P. Xiao C. FL. 1993) pp.P. Proc. N. and Opalka E. Gold R. White. eds.EPRI Licensed Material References Xiao C. and J.R. Conf.C.. Memorial University of Newfoundland. 1995) pp 511-517.P. D. Eds. 12th Int. Sengers. (Materials Metals Minerals Soc. (1994) Standard partial molar heat capacities and volumes of aqueous divalent and trivalent ions from measurements near 25°C. and Simonen E.Water Reactors. J. (1993) Magnetite stability in aqueous sodium phosphate solution at elevated temperatures. Proc. Xiao C. on Properties of Water and Steam... 929-935. Bellows.. H. and Tremaine P. on Properties of Water and Steam (Orlando.R. 7-8 .B. Ziemniak S. Also cited as Knolls Atomic Power Lab Report KAPL-4735 (1992).V.Y. 12th Int. PhD Thesis. Neumann.E. Conf.

T. A.Ho T. enthalpy and entropy are related through the well known identity: ∆fG i.T.T.T. p r A. K.1.1 to A. B. For the hypothetical formation reaction of A2B from the elements A and B. p r A. p = G o 2 B. Gibbs energies and enthalpies of formation at high temperature and pressure are defined as ∆ f G o 2 B. aqueous and gaseous reactants and products. Solids and Gases A.p = ∆fH i. for the formation of solid or gaseous reaction products may be calculated from the standard Gibbs energies of formation of the solid.T. p .T. B. pr.2 Ho T.3 are reprinted from Quinlan (1996) with permission of the author. The standard Gibbs energies and enthalpies of formation at high temperature and pressure are defined in terms of the formation of the species or compound from the elements in their reference states at the same temperature and reference pressure. A A ∆f Ho 2B.2 G o T.T.p o o o (A-1) (A-2) (A-3) where the entropy of formation of compound (i) is given by: A-1 . p = Ho 2 B. Solids and Gases Sections A.p − Τ∆fS i.G o T.EPRI Licensed Material A THE THERMODYNAMICS OF AQUEOUS SPECIES. p . p r . SOLIDS AND GASES The Thermodynamics of Aqueous Species.1 Standard State Properties of Aqueous Species. p r .1 Solids and Gases Equilibrium constants. A A Gibbs energy.

T ∫ ∆ f Co /T dT + ∫ ∆ V o dp p p Tr pr T p (A-5) Ionic solids display only slight variations in volume with temperature and pressure. liquids. p r (T .p = ΣνjSoj.T. p . B.2 Ho T r .15 K and 1 bar through the heat capacity change of formation ∆fCp.G o T r . B. The heat capacities of solids. p r A.p are the entropies of the elements (j) multiplied by stoichiometric coefficients (νj) required to form compound (i) from its constituent elements. Standard Gibbs free energies and enthalpies of formation are used extensively by chemists.∆ f So r .T. (1978) have recommended the use of so-called “apparent” Gibbs energies of formation. Soj.p In Eq.Ho T r .p° requires a knowledge of the heat capacity. and gases are commonly described by the MaierKelley equation (1932) Cp = a + bT + cT-2 (A-6) Expressions for the heat capacities and volume functions for aqueous species are more complex. p r . T T ∫ Tr T ∆ f Co dT . p r A. ∆aGT.2 G o T r .T. Benson (1968) and Helgeson et al. A A ∆a Ho 2 B.p r . These are described in the following section.EPRI Licensed Material The Thermodynamics of Aqueous Species. p . Solids and Gases ∆fSoi. There may be discontinuities in the properties of the elements at the temperatures where phase changes occur which makes the calculation difficult.T.T. Since the properties of the elements cancel in the expressions for balanced reactions. These are defined in terms of the reactions from compounds at T and p from the elements in their reference states at 298.p r . (A-4) The high temperature values of these properties are calculated from values at 298. A A The temperature dependence of ∆aGT. p = Ho 2 B.T.15K and 1 bar: ∆a G o 2 B. A-4. so that the volume may be assumed to be constant.T r ) + T. and volume of the elements in their reference states at the temperature and pressure of interest.p°. however. T° and from the volume change ∆V°: ∆ f G o p = ∆ f G o r . the calculation of ∆fGT. entropy. p = G o 2 B.p° is given by the expression A-2 (A-7) (A-8) .T.

p. Solids and Gases ∆a Go p T. Θ = 228 K is a solventdependent parameter. in which X. c1. The “HKF” equations were revised by Tanger and Helgeson (1988).p° by the following equations ∆ r G o = . = ∆ f G o r .Θ) } .EPRI Licensed Material The Thermodynamics of Aqueous Species. These may be modelled by the semi-empirical functions originally proposed by Helgeson and Kirkham. At constant pressure. The terms ωTX and ωQ are the electrostatic contributions to the standard molar heat capacity and standard molar volume according to the Born equation.1.2° and V2° for aqueous species.RT ln K ∆ r G o = ∑ ∆ a G o (products) . the revised HKF equations take the form Co = c1 +{ c2 /(T. The temperature dependence of standard partial molar properties for aqueous species is controlled by ion-water interactions.∑ ∆ a G o (reactants) T T T = ∑ ∆ f G o (products) . p . Cp. Equations A-3 and A-9 require the use of the standard partial molar heat capacity and standard partial molar volume. (1976) and Helgeson. v1 and v2 are species-dependent fitting parameters.T ∫ C o /T dT + p Tr T pr ∫ p V o dp (A-9) Equilibrium constants are related to the Gibbs energies of reaction ∆rGT. Q and ω are given by Q = ε -1 ( ∂ ln ε /∂ p)T X = ε -1 [(∂2 ln ε /∂ T 2)p .( ∂ ln ε /∂ T )2 ] p and A-3 (A-14) (A-15) . 2 (A-12) (A-13) Here.ω Q.∑ ∆ f G o (reactants) T T (A-10) (A-11) A.2 Vo = v1 +{ v2 /(T.T r ) + T r T r ∫ Tr T C o dT p .Θ )2 } + ω TX. Kirkham and Flowers (1981).2 Aqueous Species By definition. p (T . c2.So r .

a3 and a4 are species-dependent fitting parameters.p r ) + a 4 ln  + ωTX ψ + pr  (T . although it was physical meaning only for aqueous ions. For example. Solids and Gases ω =Z2 η/re (A-16) where ε is the static dielectric constant of water. for the reaction: A-4 . p) = a1 + 1 a2 + ψ + p (T .6603 ⋅ 10-5 cal ⋅ m-1⋅mol-1 (6. re = rcryst for anions) (Shock and Helgeson.ω Q   Cp = c1 + o (A-17) o V (T. and re is an effective electrostatic radius of the ion (re = rcryst + 0.2 Activity Coefficients in High Temperature Water A model for the activity coefficients of the aqueous species is required to describe solubility equilibria at finite molalities. The equations cited are the basis for the thermodynamic modelling code SUPCRT92 (Johnson et al. Xiao (1997) and Xiao and Tremaine (1994) have made a preliminary assessment of the application of more detailed semi-continuum solvation models by Abraham and Marcus (1986). For neutral species such as gases. References describing the derivation of these equations and the practical application to modelling high temperature equilibria were summarized by Shock et al. Neglecting the pressure dependence of ω.. gases. The calculations confirm that standard-state and other terms arising from a rigorous treatment of the solvation cycle are small compared with the contribution of configurational hydration to the empirical terms in Equations A-17 and A-18 at temperatures well-removed from 25°C. SUPCRT92 is an interactive Fortran 77 program with a thermodynamic database containing many minerals. Z is the ionic charge. ω was used as an adjustable parameter to fit experimental data. η = 1. ψ is a solvent parameter equal to 2600 bar.Θ) (A-18) Here a1. A. and aqueous species. a2. the full expressions to describe the variations in Cp° and V° with temperature and pressure take the form ψ+p  2T  c2 a 3 (p . (1992).Θ )2 (T . 1988). Goldman and Bates (1972) and others.94 Z for cations.9466 ⋅ 10-5 J⋅m-1⋅mol-1). The theoretical basis is consistent with Equations A-12 to A-18 described above. 1992).Θ )3   a4  a 3 + ψ + p  .EPRI Licensed Material The Thermodynamics of Aqueous Species.

in which the activity coefficients at a given ionic strength are assumed to be scaled to those of NaCl.1990) has proposed the use of a “model substance” approach in this region. these are very specific for each ion and relatively complex semi-empirical models are required to describe the activity coefficients and other excess properties (Pitzer. was considered most appropriate for this study. the values for γ±(NaCl. the long range hydration effects that control the specific nature of ion-ion interactions are weakened. which is usually unity. aq) Therefore the equilibrium constant for Reaction A-19 can be written as follows: K = m(A+. Lindsay’s model is used in the EPRI computer code MULTEQ (Lindsay. 1989. At temperatures above about 150°C. aq)2 ⋅ γ(B2-. Baes and Lindsay. Q. (A-19) (A-20) (A-21) (A-22) The activity coefficients reflect the effect of ion-ion interactions.EPRI Licensed Material The Thermodynamics of Aqueous Species. According to this model the activity coefficients of AZ+ ions are assumed to be given by: γ|z| = [ γ ± (NaCl) ]z 2 (A-23) This expression is consistent with the Debye-Hückel limiting law. aq)2⋅ m(B2-. To be consistent with the EPRI chemical equilibrium model MULTEQ. 1991). 1992) which is used to describe crevice corrosion in high pressure boilers and. 1995. is described in the following form: Q = m(A+. aq)2 ⋅ m(B2-. aq) were calculated using the Meissner equation (Lindsay.. 1989).(aq) ← the equilibrium quotient. Solids and Gases A2B → 2A+ (aq) + B2. At low temperatures. aq)/ a(A2B)] where a(A2B) is the activity of the solid. aq)/ a(A2B) log K = log Q + log [γ(A+. Alexander et al. aq) ⋅ γ(B2-. and ions of the same charge display much more consistent behaviour (Holmes and Mesmer. aq)2 ⋅ γ(A+. Lindsay (1989. 1983). therefore. rather than the more accurate A-5 .

Because Eqn. consistency with other data in the database is much more important than the accuracy of J±(NaCl. 1996)..EPRI Licensed Material The Thermodynamics of Aqueous Species. 1996.Q/(Q+z+2-Q-z-2)] (A-26) The effect of pressure on the activity of water is negligible. except in cases of extreme temperatures and concentrations.NaCl. aw may be calculated from the Gibbs-Duhem equation.  ∂ ln a w  Vw   ∂p  = RT   T (A-27) A-6 . and may be corrected by following relationship: in which Vw is the partial molar volume of water in the solution. A-23 is based on the approximate model substance approach. The osmotic coefficient of water. Each integral in the sum of integrals is evaluated for the range of total concentration from zero to the solution of interest. I) + 0. and the subscript x on the derivative in the right-hand side indicates that the species distribution is held fixed.018015 φ∑ mi ) sol (A-25) Application of Equations A-23 to A-25 leads to the following correlation between the activity of water in the electrolyte solution of interest aw(AQz+BQz-) and the activity of water in the “model” NaCl solution at the same ionic strength aw(NaCl): ln aw(AQz+BQz-. and the activity of water.03603 I [1. Solids and Gases formulation by Archer (1992) which was used in the earlier work (Quinlan. Tremaine et al. The activity of water is given by: a w = exp( −0.I) = ln(aw. through the expression   1  d ln γ i  ∑ mi φ −1= ∑ sol mi  d ∑ m  d∑ mi mi i ∫   i ∑ 0  i i x sol (A-24) The term 6sol mi is the total concentration of all dissolved constituents in the solution of interest. I. aq) itself.

δ12)H(T)] ln F(T) = -1.30 + 9.EPRI Licensed Material The Thermodynamics of Aqueous Species. (A-31) (A-32) (A-33) (A-34) A-7 . ln ϕ2∞ = F(T) +(Tc2/pc2) [G(T) . ϕ2 can be replaced by its value at infinite dilution ϕ2∞ .94ω) ln G(T) = -15. Therefore the final equation for the activity of inert gas has the following form: a(H2. gas) = ϕ2 p(H2)/p0 (A-29) Here ϕ2 is the fugacity coefficient of hydrogen gas in the vapour phase and p0 is the standard state pressure equal to 1 bar. (1994) proposed a relatively simple expression for ϕ2∞ for nonpolar gases in mixtures with H2O vapour.gas) are the activity of dissolved hydrogen in the aqueous phase and the fugacity of hydrogen gas in the vapour phase.81429.0184exp(4.aq) = Kp. based on the Peng and Robinson (1976) equation of state.aq) and f(H2.3 Solubility of Gases in Aqueous Electrolyte Solutions At Elevated Temperatures The solubility of a nonreactive gas such as hydrogen in water may be expressed through the equilibrium constant Kp.94ω) .T (H2 (gas) → H2 (aq)): ← Kp.525υ . and the Pitzer acentric factor ω which is specific for each solute. Solids and Gases A.T ϕ2∞ p(H2)/p0 (A-30) Alvarez et al. This treatment requires only the known critical parameters of the solute gas (Tc2.exp(-54.gas) is related to the partial pressure of hydrogen in the gas phase p(H2) as follows: f(H2. The fugacity of hydrogen f(H2.22.0(υ-1)4 where υ = T/700 and ω = υ .68 + 14. In the case of nonreactive nonpolar gas with weak interactions between the molecules of solute gas and water in vapour phase.(pc2α2)1/2 (1.87υ .0(υ-1)4 ln H(T) = -12. a binary mixing coefficient (δ12) which describes the solute-solvent interactions.T = a(H2. aq) / f(H2. gas) (A-28) where a(H2. pc2).0.8.

In dilute binary electrolyte solutions. is approximately equal to unity except in strong electrolytes. making the logaritm of the solubility linearity dependent on salt concentration.aq) by the expression m(H2.EPRI Licensed Material The Thermodynamics of Aqueous Species.aq)/γ(H2. Typical strong inorganic electrolytes decrease the solubility of nonreactive gases in water. A-8 .aq). Solids and Gases The solubility is related to a(H2.129 is constant over the temperature range 25 to 100°C.aq) = a(H2. the expression for the activity coefficient of dissolved gases becomes: ln γ = ks m (A-36) where ks is the salting coefficient and m is the molality (mol kg-1) of the electrolyte.aq) (A-35) where the activity coefficient. γ(H2. For the dissolution of hydrogen in the KOH-H2O system ks = 0.

EPRI Licensed Material B THERMODYNAMIC CONSTANTS FOR THE SODIUM/PHOSPHATE/IRON/WATER SYSTEM B-1 .

mol H (aq) OH (aq) H2(aq) H2(g) O2(g) O2(aq) H2O (l) H3PO4 (aq) H2PO4 (aq) HPO4 (aq) PO4 (aq) Na (aq) Fe3O4(s) Fe2O3(s) SIHP (s) model I SIHP (s) model II Maricite (s) model I Maricite (s) model II + 32- /cal.mol K 0 -2.560 13.940 80.712 38.9 6.6 -6.0 18.0 56.9 7.9 -58.mol 0 -4.600 -8.040 16.21 32.2 30.274 122.5 18.0 -114.5 -37595 4236 0 0 3954 -56688 -273100 -270140 -260310 -243500 -62591 -242574 -178155 -847221 -824594 -347471 -341758 -54977 -1000 0 0 -2900 -68317 -307920 -309820 -308815 -305300 -57433 -267250 -197720 -915590 -862428 -375676 -362151 B-2 .2 44.2 46.20 /cm .0 23.234 49.3 25.2 122.9 4.5 34.1 48.800 31.7 25.0 68.000 21.3 34.3 -1.8 183.000 13.830 20.96 34.029 26.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-1 o Standard state properties at 25 C and 1bar.000 -53.9 /cal mol K 0 -32.3 9.3 68.524 30.1 36. Species + ∆fG 0 o -1 ∆fH 0 o -1 S o -1 -1 V 3 o -1 Cp o -1 -1 /cal.3 0 0 30.mol /cal.0 58.4 -32.9 46.6 39.

2 21.20 78.55 0.52 7.00 18.16 23.40 -3.12 -0.49 c x 10-5 /cal mol-1 K 0.68 -2.49 21.88 40.60 48.0 3.78 1.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-2 Maier-Kelley coefficients for heat capacities of solids and gases.24 H2 (g) O2 (g) Fe2O3 (s) Fe3O4 (s) SIHP(s) Maricite(s) B-3 .57 b x 103 /cal mol-1 K-2 0.87 25. Species a /cal mol-1K-1 6.

5 5.5 7.3 15.2 14.013 2.7 12.9 -19.3 10.3 15.247 7.536 25.591 ∆G o -1 ∆H o -1 ∆S o -1 -1 ∆V 3 o -1 ∆Cp o -1 -1 /cal mol -16133 -16224 -16347 -16498 -16673 -16873 -17094 -17337 -17599 -17880 -18176 -18471 -18722 -18795 /cal mol -15240 -14789 -14395 -14019 -13645 -13265 -12882 -12499 -12108 -11726 -11484 -11870 -14583 -30745 /cal mol K 2.2 1.9 11.5 6.00 50.043 6.5 6.00 75.7 -3027.4 9.00 150.3 5.6 /cal mol K 20.6 -301.5 15.917 0.3 3.834 0.2 3.000 1.9 4.1 10.00 300.1 15.5 8.211 ρH2O /g.975 0.655 0.000 1.825 10.00 275.3 3.00 225.9 14.00 125.972 10.336 8.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-3 Standard state properties of the reaction: H3PO4(aq) + OH (aq) → H2PO4 (aq) + H2O(l) ← t /°C 25.0 3.918 15.152 8.6 -30.cm 0.759 0.757 8.00 100.458 165.2 /cm mol 5.841 6.939 0.799 0.008 7.5 2.3 6.5 15.2 7.8 4.00 175.9 15.712 0.721 7.431 85.958 0.261 9.865 0.00 325.662 9.997 0.6 -52.376 59.1 11.575 -3 log K 11.00 250.320 4.714 8.1 B-4 .892 0.988 0.000 1.2 16.3 -275.838 120.00 350.00 200.2 7.469 7.479 39.5 4.00 p /bar 1.

834 0.997 0.7 -13.1 -9.597 2.757 8.5 -13.967 4.cm 0.376 59.365 2.4 -10.939 0.4 -10.00 275.6 -10.7 -12.1 -8.479 39.7 -6.000 1.655 0.3 /cal mol K -0.975 0.838 120.790 6.5 -10.00 175.510 4.000 1.00 325.7 -10.5 -0.00 50.7 -5.7 958.000 1.4 69.105 3.965 ∆G o -1 ∆H o -1 ∆S o -1 -1 ∆V 3 o -1 ∆Cp o -1 -1 /cal mol -9263 -9004 -8744 -8482 -8217 -7948 -7675 -7397 -7112 -6819 -6515 -6201 -5887 -5602 /cal mol -12335 -12349 -12372 -12408 -12461 -12534 -12627 -12747 -12915 -13154 -13456 -13695 -13445 -9558 /cal mol K -10.9 -11.120 2.417 3.211 ρ H2O /g.8 -2.712 0.917 0.00 300.988 0.865 0.4 /cm mol -3.2 -5.2 -1.00 125.575 -3 log K 6.7 B-5 .8 -7.151 1.958 0.00 200.00 p /bar 1.5 -3.799 0.6 -9.1 -9.458 165.3 -11.00 100.431 85.892 0.918 15.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-4 2Standard state properties of the reaction: H2PO4 (aq) + OH (aq) → HPO4 (aq) + H2O(l) ← t /°C 25.6 -13.5 -8.3 -10.743 3.00 250.536 25.00 75.1 -12.00 350.00 225.7 -1.0 -3.6 -6.759 0.489 4.00 150.5 -15.320 4.4 -11.2 -11.1 -11.849 2.6 -8.3 -4.013 2.9 57.089 5.1 -12.

9 -15.958 0.013 2.410 -1.cm 0.918 15.917 0.431 85.00 75.8 -9.4 /cal mol K -5.00 275.997 0.1 -17.263 -2.1 -26.00 350.5 -7.673 1.00 125.9 -25.654 -1.939 0.5 -31.2 -26.575 -3 log K 1.2 -17.00 325.1 -11.1 10.355 ∆G o -1 ∆H o -1 ∆S o -1 -1 ∆V 3 o -1 ∆Cp o -1 -1 /cal mol -2283 -1634 -975 -306 374 1065 1768 2485 3214 3959 4719 5480 6194 6714 /cal mol -9825 -9959 1009 -1024 -1042 -1063 -10875 -11146 -11479 -11887 -12247 -12002 -9214 9409 /cal mol K -25.089 -2.000 1.975 0.7 -26.0 -27.179 -0.881 -2.7 -19.550 -0.00 225.1 313.00 300.6 -21.211 δH2O /g.458 165.862 -1.6 B-6 .6 -22.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-5 23Standard state properties of the reaction: HPO4 (aq) + OH (aq) → PO4 (aq) + H2O(l) ← t /°C 25.759 0.1 /cm mol -13.8 -5.0 -27.6 -6.757 8.376 59.000 1.00 50.6 -27.838 120.988 0.799 0.00 150.5 -29.00 200.1 -10.000 1.865 0.7 -20.3 48.2 -30.612 0.2 -5.8 -30.00 175.7 -24.205 -0.9 -16.3 3749.4 332.105 0.7 -26.4 -28.479 39.0 4.148 -1.655 0.0 -28.00 p /bar 1.7 -18.4 -8.320 4.892 0.536 25.834 0.712 0.00 250.1 -29.00 100.

0 56.098 -3.4 -7.7 27.6 1421.2 94.504 -2.479 39.6 29.1 26.975 0.211 ρ H 2O /g.00 75.1 -9.0 28.9 30.431 85.892 0.9 -11.9 39.00 125.00 350.3 /cm /cal K 33.247 -2.00 300.918 15.4 -15.2 48.977 -2.917 0.997 0.cm 0.00 100.044 -2.00 250.865 0.00 p /bar 1.810 -2.132 -3.838 120.0 -12.939 0.3 26.458 165.757 8.5 26.0 33.9 235.0 25.00 325.4 28.0 28.536 25.3 -4.00 50.655 0.3 0.575 -3 log K -3.8 9.759 0.4 73.384 -2.7 -3.00 200.712 0.1 26.105 -3.1 B-7 .8 3.376 59.2 30.1 -1.3 188.5 27.5 34.00 275.958 0.715 -2.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-6 Standard state properties of the reaction: H2 (g) → H2(aq) ← t /°C 25.8 -6.000 1.00 150.0 31.00 175.988 0.7 26.613 -2.000 1.0 32.898 -2.799 0.834 0.8 41.138 -3.013 2.000 1.067 ∆G o ∆H o ∆S o -1 ∆V o 3 ∆Cp o -1 /cal 4236 4640 4989 5289 5546 5763 5942 6084 6189 6256 6280 6253 6150 5895 /cal -1000 -241 446 1105 1757 2417 3100 3823 4617 5536 6694 8374 11508 21592 /cal K -17.320 4.9 25.00 225.

00 300.00 325.5 1914.958 0.1 /cm /cal K 948.382 79.5 417.9 3775.799 0.712 0.975 0.988 0.8 19630.275 23.320 4.4 6408.838 120.6 1205.8 5734.939 0.7 747.289 51.00 100.0 700.3 710.013 2.997 0.2 364.917 0.431 85.249 45.3 798.00 75.633 39.2 721.1 68955.5 1127.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-7 Standard state properties of the reaction (Model I): 2+ 3 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2.2 691.00 200.000 1.9 1932.8 9371.00 250.536 25.0 B-8 .8 946.458 165.865 0.1 472.7 1020.8 933.2 743.000 1.00 p /bar 1.759 0.7 2689.214 28.1 2566.456 18.509 ∆G o ∆H o ∆S o -1 ∆V o 3 ∆Cp o -1 /cal -6024 -12991 -21436 -31203 -42291 -54821 -68968 -84973 -103230 -124378 -149338 -179337 -216368 -266626 /cal 67028 87635 105861 124815 146331 171931 203088 242482 295604 370949 480570 644933 929075 1656175 /cal K 243.5 891.00 225.2 799.211 ρ H 2O /g.541 68.00 175.00 50.918 15.00 125.cm 0.5 1483.314 33.834 0.000 1. (Na4/3H2/3O) (s) + 5 H2O ← t /°C 25.655 0.4 3997.415 8.5 729.00 150.479 39.959 59.9 802.9 606.7 12193.786 13.1 1828.7 1393.4 1437.054 93.376 59.575 -3 log K 4.00 275.757 8.0 1148.3 3085.892 0.8 534.7 310.00 350.

375 26.9 2528.7 1020.799 0.7 1305.431 85.8 5734.3 1560.00 300.9 1932.3 798.00 100.838 120.865 0.5 1483.5 891.00 225.0 700.988 0.000 66.9 802.6 979.00 125.7 2689.479 39.1 1828.247 -17.6 1205.458 165.4 6408.209 39.7 1414.5 1031.00 p /bar 1.00 200.536 25.211 ρ H 2O /g.4 1220.5 1762.759 0.7 1393.047 96.892 0.135 12.575 -3 log K -95.939 0.655 0.641 -52.00 250.997 0.712 0. (Na4/3H2/3O) (s) + 5 H2O ← t /°C 25.642 53.958 0.757 8.0 /cm /cal K 948.917 0.cm 0.9 3775.5 1087.659 81.000 1.803 115.8 19630.00 275.5 729.9 2051.2 1149.481 -34.4 3997.00 75.0 B-9 .00 175.376 59.00 150.013 2.1 68955.7 12193.7 747.1 2566.320 4.8 3699.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-8 Standard state properties of the reaction (Model II): 2+ 3 Fe2O3(s) + 26 Na (aq) + 12 HPO4 (aq) + 2OH (aq) → 6 Na3Fe(PO4)2.918 15.933 ∆G o ∆H o ∆S o -1 ∆V o 3 ∆Cp o -1 /cal 129738 107409 83603 58475 32025 4133 -25375 -56742 -90360 -126870 -167191 -212552 -264944 -330564 /cal 386000 406607 424833 443787 465303 490903 522060 561454 614576 689921 799542 963905 1248047 1975147 /cal K 858.00 350.8 9371.000 1.2 743.00 50.579 -2.00 325.975 0.099 -72.000 1.2 721.8 933.2 924.834 0.4 1127.3 710.

1 61.7 55.892 0.6 134.000 1.6 166.6 122.7 65.00 200.013 2.388 5.536 25.00 300.00 75.6 84.079 11.013 7.376 59.4 49.00 100.918 15.000 1.776 ∆G o ∆H o ∆S o -1 ∆V o 3 ∆Cp o -1 /cal -4845 -5884 -7059 -8368 -9817 -11421 -13201 -15184 -17414 -19960 -22921 -26432 -30709 -36429 /cal 6718 8537 10312 12272 14569 17344 20741 25044 30838 39042 50963 68835 99775 179351 /cal K 38.1 67.3 64.655 0.00 350.640 8.979 4.00 225.3 427.8 2142.2 100.0 7631.7 112.917 0.0 346.431 85.00 150.865 0.799 0.8 202.1 218.1 88.338 9.00 p /bar 1.00 275.00 50.458 165.0 69.9 411.0 623.7 123.898 6.437 7.1 153.3 102.939 0.000 1.901 5.834 0.220 12.7 279.6 1019.8 75.1 1330.575 -3 log K 3.139 10.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-9 Standard state properties of the reaction (Model I): 2+ Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH + H2O ← t /°C 25.838 120.712 0.7 66.988 0.6 84.5 44.551 3.8 71.431 4.958 0.9 96.479 39.211 ρ H 2O /g.997 0.cm 0.8 73.320 4.00 125.757 8.0 B-10 .759 0.00 250.8 691.00 325.00 175.8 152.8 285.2 199.2 78.975 0.1 /cm /cal K 79.

479 39.000 1.00 225.012 -6.8 202.918 15.6 1019.785 13.988 0.2 78.6 84.00 75.00 350.684 -0.655 0.6 122.3 64.211 ρ H 2O /g.3 133.00 325.00 300.712 0.00 p /bar 1.958 0.2 244.536 25.0 128.6 424.320 4.575 -3 log K -9.829 5.144 57919 61316 65619 71413 79617 91538 109410 140350 219926 /cal K 117.997 0.2 199.00 200.431 85.376 59.0 623.834 0.013 2.8 285.9 411.4 154.939 0.757 8.121 3.2 163.7 123.838 120.7 65.7 279.975 0.574 15.1 123.917 0.2 213.000 1.7 /cm /cal K 79.3 191.00 150.892 0.2 100.8 152.860 -1.5 175.00 125.7 66.458 165.8 71.000 1.8 2142.7 139.00 175.8 73.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-10 Standard state properties of the reaction (Model II): 2+ Fe3O4(s) + 3 Na (aq) + 3 HPO4 (aq) + H2(aq) → 3 NaFePO4(s) + 3 OH + H2O ← t /°C 25.799 0.566 10.295 2.1 153.00 250.00 275.0 7631.450 7.283 -3.00 100.017 8.865 0.cm 0.7 146.1 88.140 11.1 1330.8 691.7 296.0 B-11 .3 102.00 50.724 ∆G o ∆H o ∆S o -1 ∆V o 3 ∆Cp o -1 /cal 12294 9290 6150 2876 -538 -4107 -7852 -11800 -15995 -20506 -25432 -30908 -37150 -44835 /cal 47293 49112 50887 52847 55.0 69.3 427.759 0.

939 0.458 165.1 -3.834 0.0 28.8 -1.7 0.479 39.00 250.00 300.000 1.712 0.211 ρ H 2O /g.9 -2.EPRI Licensed Material Thermodynamic Constants for the Sodium/Phosphate/Iron/Water System Table B-11 Standard state properties of the reaction: 2 Fe3O4(s) + H2O → 3 Fe2O3(s) + H2 (aq) ← t /°C 25.933 -4.2 /cm 9.00 275.cm 0.376 59.00 p /bar 1.460 -5.892 0.00 200.1 17.4 1.682 -4.1 20.536 25.00 125.7 19.2 11.7 14.191 -4.918 15.838 120.320 4.00 100.999 -7.00 225.746 -5.1 10.958 0.3 212.997 0.4 18.865 0.8 18.00 150.431 85.575 -3 log K -8.2 B-12 .000 1.0 /cal K 24.013 2.00 175.148 ∆G o ∆H o ∆S o -1 ∆V o 3 ∆Cp o -1 /cal 11607 11827 12007 12152 12266 12351 12409 12440 12446 12425 12373 12280 12124 11827 /cal 8657 9214 9713 10188 10654 11118 11590 12083 12621 13251 14079 15371 18039 27511 /cal K -9.975 0.6 159.917 0.7 -0.5 20.7 3.5 18.9 47.0 11.0 -6.655 0.5 -5.733 -6.6 19.7 11.051 -5.430 -4.00 75.8 -8.0 1383.5 10.379 -6.2 5.9 10.3 24.7 77.0 25.00 350.9 12.4 23.4 11.7 41.00 325.000 1.799 0.757 8.6 11.537 -7.00 50.117 -6.988 0.508 -7.759 0.

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