LA-13174-MS Different Nonideality Relationships, Different Databases and Their Effects on Modeling Precipitation from Concentrated Solutions Using Numerical Speciation Codes RECEIVED SFP 26 1996 osTl MASTER NATIONAL LABORATORY Los Alamos National Laboratory is operated by the University of California {Jor the United States Department of Energy under contract W.-7405-ENG-36.‘An Affirmative Action/Equal Opportunity Employer ‘This report sas prepare as an account of work sponsored by an agency ofthe United Stator Government. Neither The Regents of the University of California, the United States rere ay eee or oft np aes nora, eres (or implied or assumes any legal lily or responsiblity forthe accuracy, completeness oF ssfulness of any information, apparatus, product, or proces disclosed, or represents that ts tse woul not infringe roatly ened rights. Reference herein foamy Spec commercial product, pres, service by trade name, trademark, manfacturer, or eters, doesnot hecessaily constitute or imply its endorement, recommendation, favoring by Phe Regents ofthe Unicesty of California, the United Stats Government, or any agency theres. The ies and opinions of ators expressed herein do ot necessarily sate o reflect thse of ‘The Regents of the Uniersity of California, he United States Goverment, or any agency ‘ref. The Los Alamos National Laboratory strongly supports acide fed and @ researcher's right fo publish; therefore, the Laboratory asa intttion doesnot endorse the viewpoint of «publication or uarante is tecnica correctness.LA-13174-MS uc-905 Issued: August 1996 Different Nonideality Relationships, Different Databases and Their Effects on Modeling Precipitation from Concentrated Solutions Using Numerical Speciation Codes Lee F. Brown Michael H. Ebinger MASTER DISTRIBUTION OF THIS DOCUMENT {$ UNL! IS Los Alamo: NATIONAL LABORATORY Los Alamos, New Mexico 87545DISCLAIMER Portions of this document may be illegible in electronic image products. Images are produced from the best available original document.vi CONTENTS: FIGURE TABLES NOMENCLATURE ‘ACRONYMS GLOSSARY ABSTRACT EXECUTIVE SUMMARY GOAL OF INVESTIGATION METHODS USED IN THIS STUDY NUMERICAL EQUILIBRIUM OR THERMODYNAMICS SPECIATION CODES A. Overview of Numerical Equilibrium Codes B. Calculation of Activity Coefficients ©. Uncertainties in Numerical Equilibrium Codes ‘THE EQ3/6 THERMODYNAMICS SPECIATION CODES Attributes of the EQ3/6 Codes. Codes and Files in the EQ3/6 System, Different Relationships Available in the EQ3/6 Codes for Calculating Activity Coefficients. Different Databases Embedded in the EQ3/6 Codes. Databases and Activity-Coefficient Relationships Used in this Study. mo o> PROBLEM STATEMENTS AND PURPOSES OF PROBLEMS Precipitation Problem #1-Precipitation of Calcium Hydroxide (Portlandite) by Mixing Concentrated Solutions of Calcium Chloride and Sodium Hydroxide Precipitation Problem #2--Possible Precipitation of Calcium Hydroxide from Mixing Dilute Solutions of Calcium Chloride and Sodium Hydroxide with a Concentrated Sodium Chloride Solution Precipitation Problem #3--Simultaneous Precipitation of Calcium Sulfate (Gypsum) and Calcium Hydroxide (Portlandite) by Mixing Solutions of Calcium Chloride, Sodium Sulfate, and Sodium Hydroxide Precipitation Problem #4~-Evaporation of Supematant Solution Remaining from Simultaneous Precipitation of Calcium Hydroxide and Calcium Sulfate page vi vil vii villVIL vit Figure 1. vi RESULTS, - Precipitation Problem #1 Precipitation Problem #2 Precipitation Problem #3 Precipitation Problem #4 Mass Balances Solubility Products mmoop> DISCUSSION ‘A. Comparison of Differences in Predicted Concentrations with Accuracy of Models and Data B. Approximate invariance of the Amounts of Ca(OH) Precipitated in Results of Problem #1 but not in Results of Problem #2, 1. The approximate invariance of the amounts of Ca(OH)2 precipitated in Problem #1 2. The significant variations in the amounts of Ca(OH): precipitated in Problem #2 ©. Approximate invariance of the Amounts of Ca(OH)2 and CaSO42H.O Precipitated in Results of Precipitation Problem #3, 4. The approximate invariance of the amount of Ca(OH) precipitated in Problem #3. 2. The approximate invariance of the amount of CaS04-2H,0 precipitated in Problem #3. D. General Applications of the Sensitivity Factors. 4. Qualitative and quantitative aspects. 2. Future directions. CONCLUSIONS ACKNOWLEDGMENTS. APPENDIX A Problem Statements of Four Simple Precipitation Problems and Sample Problem Calculations for Ideal Solutions APPENDIXB Sample Calculation of Solubility Product from Free Energies of Formation APPENDIXC Modeling Multicomponent Precipitation from Nonideal Solutions APPENDIX D Derivation of Equation (VIII-33) REFERENCES FIGURE ‘The flow of information among the computer codes EQPT, EQ3NR, and EQ6. Computer codes are represented by ovals, files by rectangles. page 10 "1 12 12 13 13 14 4 15 15 Bt ct D4 RA 22Table 1. Table 2, Table 3. Table 4, Table 5. Table 6. Table 7. vii page TABLES Major Characteristics of Chemical Equilibria Codes 23 ‘Major Characteristics of the Five EQ3/6 Data Files 24 Results from Solving Precipitation Problem #1--Precipit of Portlandite from a Concentrated Solution 25 Results from Solving Precipitation Problem #2~Possible Precipitation of Portlandite 26 Results from Solving Precipitation Problem #3--Simultaneous, Precipitation of Gypsum and Portlandite 20 Results from Solving Precipitation Problem #4—Evaporation ‘of Water from Supematant Solutions Resulting from Problem #3 28 Mass Balances 30 Table C-1. Effects on Xea/Xdea) and do/dioe: of Concentration, ‘Solubility-Product Ratio, and Activity-Coefficient Ratio for the Precipitation Model C3 NOMENCLATURE, (Dimensions given below are typical dimensions. Sometimes different units are used in the text.) Roman symbols a ‘The thermodynamic activity of substance i, dimensionless. Kup The solubility product, (molL)” L Liter. M Molar. Refers to the molarity of a solution, e.g., 1.0 Mis @ 1.0 molar solution, PKep The negative of the logarithm of the solubility product. 0 The sum of the exponents in the solubility product. x ‘The amount of Ca‘* ion precipitating as Ca(OH). in Precipitation Problems #1-#3, mol/L. y ‘The amount of Ca’ ion precipitating as CaSO,-2H,0 in Precipitation Problem #3, mol, Greek symbols B ” 5 XeaKzeu in discussion of Precipitation Problems #1, #2, and #3, and in Appendix C. ‘Ywo/¥iea in discussion of Precipitation Problem #3 and in Appendixes C and D. The activity coefficient of substance i, Limo. A.combination of activity coefficients. In Precipitation Problems #1 and #2, = = Yoau.12u- In Precipitation Problem #8, & = ¥sox. / Yowvill Subscripts i Relating to substance i orto the i" component in a reaction. ideal Relating to an ideal solution, or calculated using ideal-solution theory. real Relating to a real solution, or calculated using real-solution theory. 0 Initial value or entering value before precipitation occurs. Also, the value for the first term Taylor series expansion or an ideal-solution value. ‘Superscripts + ‘An jon with a single positive charge. ++ Anion with a double positive charge. - ‘An ion with a single negative charge. - ‘An ion with a double negative charge. Other Symbols {1 Concentration, mol/L In the tite or suffix of a computer file, the asterisk stands for any ttle or suffix. Titles of computer codes are entirely capitalized, tiles of computer files appear in bold-faced type. ‘ACRONYMS DH Debye-Hiickel. LUNE Lawrence Livermore National Laboratory. RHS Right-hand side of an equation or expression. wert with respect to GLOSSARY Anhydrite The mineral calcium sulfate (CaSO,) without water of hydration. Antarcticite ‘The mineral CaCl-6H,0. Glauberite ‘The mineral NazCa(SO,),. Gypsum Hydrated calcium sulfate, CaS0-2H,0. Halite Native salt, NaCl. Mirabitite Hydrated sodium sulfate, NagSO,10H,0. Portlandite The mineral calcium hydroxide, Ca(OH). Thenardite ‘The mineral sodium sulfate, Na;SOx,DIFFERENT NONIDEALITY RELATIONSHIPS, DIFFERENT DATABASES AND THEIR EFFECTS: ON MODELING PRECIPITATION FROM CONCENTRATED SOLUTIONS USING NUMERICAL SPECIATION CODES by Lee F. Brown and Michael H. Ebinger ABSTRACT Four simple precipitation problems are solved to examine the use of numerical equilibrium codes. ‘The study emphasizes concentrated solutions, assumes both ideal and nonideal solutions, and employs different databases and different activity-coefficient relationships. The study uses the EQ3/8 numerical speciation codes. The results show satisfactory material balances and agreement between solubility products calculated from free-energy relationships and those calculated from concentrations and activity coefficients. Precipitates show slightly higher solubilities when the solutions are regarded as nonideal than when considered ideal, agreeing with theory. When a substance may precipitate from a solution dilute in the precipitating substance, a code may or may not predict precipitation, depending on the database or activity-coefficient relationship used. In a problem involving a two-component precipitation, there are only small differences in the precipitate mass and composition between the ideal and nonideal solution calculations. Analysis of this result indicates that this may be a frequent occurrence. An analytical approach is derived for judging whether this phenomenon will occur in any real or postulated Precipitation situation. The discussion looks at applications of this approach. In the solutes remaining after the precipitations, there seems to be little consistency in the calculated concentrations and a¢ coefficients. They do not appear to depend in any coherent manner on the database or activity- coefficient relationship used. These results reinforce warnings in the literature about perfunctory or mechanical use of numerical speciation codes. 1, EXECUTIVE SUMMARY This work examines using numerical equilibrium codes to solve concentrated-solution preci problems. The work computes compositions and amounts precipitating from solution together with solution compositions in equilibrium with precipitates using different thermodynamic databases and ifferent activity coefficient relationships. ‘The consistency of thermodynamic databases is perhaps the greatest source of uncertainty in numerical calculations of chemical equilibria, Perhaps the next greatest weakness in these calculations lies in the evaluation of activity coefficients. Thus this study investigates the two largest sources of uncertainty in numerical calculations ofthis type. The EQ3/6 numerical speciation codes are the model programs implemented in this work ‘The study solves four simple problems, each emphasizing different aspects of precipitation from solution. The first problem involves precipitation ofa single substance from a concentrated solution. The second problem concems a single substance precipitating from a solution dilute in the precipitating species but concentrated in other ions. In the third problem, simultaneous precipitation of two substances from a concentrated solution occurs. The fourth problem envisions evaporation of almost all the water from the supematant liquids remaining after the predicted precipitation in the previous problem,There are six approaches to solving each problem. Two use different solubility-product sources {for ideal-solution calcul ions. Two acknowledge nonideality and employ different activity-coefficient relationships and the same thermodynamic database. The final two acknowledge nonideality and use the same activity-coefficient relationship but different databases. ‘The results ofthe first problem give a precipitate amount approximately the same for both ideal and nonideal-solution calculations, as expected. The nonideal-solution calculations predict a slightly ‘greater solubility of the precipitate, again as expected. Some calculations solving the second problem predict precipitation, some do not, with no noticeable consistency. The nonideal-solution calculations solving the third problem predict amounts of both precipitates approximately equal to those predicted by the ideal-solution calculations. There appears to be litle agreement in the calculated ion concentrations and activity coefficients in the supematant solutions. The results of the fourth problem show wide variation the precipitate amounts, showing the weaknesses of using numerical speciation codes to Predict results of evaporation campaigns without extensive knowledge of the system. Combinations of activity coefficients and ion concentrations can yield situations where ideal- Solution calculations can predict precipitate amounts from nonideal solutions. An analytical approach to comparing ideal and nonideal precipitation predictions gives a method for forecasting whether ideal precipitation predictions will be valid for nonideal solutions. ‘The lack of consistency in the calculated ion concentrations and activity coefficients and their apparent lack of dependence in any coherent manner on database or activity-coefficient relationships reinforce wamings in the literature about the use of numeric speciation codes without extensive knowledge of the system. Il, GOAL OF INVESTIGATION ‘As mentioned below in Section IV.C, numerical equilibrium computer codes have some inherent uncertainties. Perhaps the greatest uncertainty is the dependence of the results on the particular thermodynamic database being used. Another uncertainty results from the choice of activity-coefficient relationships for use in a code. It is the goal ofthis study to investigate how use of different thermodynamic databases and actvity-coefficient relationships can influence the results of modeling different precipitation scenarios. The situations studied are simple, so interpretation of the results is, unambiguous. Concentrated solutions are emphasized in this work. Il, METHODS USED IN THIS STUDY This study uses the numerical speciation code embodied in the EQ3/6 programs. As presently distributed, these codes have embedded within them several databases and different activity-coefficient relationships. They are thus well adapted to this investigation.‘The study solves four different precipitation problems. Each problem emphasizes different aspects of the precipitation process. Particular characteristics of both the precipitate and the resulting solution in equilibrium with the precipitate are determined. The study solves each problem using six different approaches. Two of the approaches assume ideal solutions, and solve the problems by simple algebra. The algebraic solutions to each problem are based on different values of the solubility products, obtained from different, but stil supposedly reliable, sources. For each problem, the four solutions that include nonideality use the thermodynamic speciation codes EQ3/6, Embedded in the codes’ software are five thermodynamic databases. Three of these were chosen for this study, and Section IV.D below discusses these. Two approaches use one of these databases, but employ different relationships for calculating activity coefficients. Another activity- coefficient relationship is used with each of the other two databases. Thus each problem is solved using three databases and three activity-coefficient relationships. Section V presents statements of the problems. Appendix A repeats the problem statements, and gives examples of the algebraic solutions for ideal-solution situations. IV, NUMERICAL EQUILIBRIUM OR THERMODYNAMICS SPECIATION CODES ‘A. Overview of Numerical Equilibrium Codes. The last 30-plus years have seen the creation of many numerical computer codes for calculating chemical equilibria in mutiple-species and multiple-phase systems. In the 20 years following the basic work of Garrels and Thompson (1962), investigators developed many programs for this purpose. The codes are based on rigorous thermodynamics principles and use various thermodynamics approaches and numerical techniques for solution of the resulting equations. Zeleznik and Gordon (1968) give a thorough review of the principles involved and the bases of the applications. Nordstrom et al. (1979) compare the characteristics of codes popular at that time and the results of two test problems using those codes. Mangold and Tsang (1991) give a later list of some of the more popular codes. Bassett ‘and Melchior (1990) also list some of the more popular codes and give an overview of then-current trends in developing these codes. The 10 years preceding this paper saw a significant decrease in the introduction of new codes (Bassett and Melchior op. cit). Rather, the emphasis was on improving existing codes, expanding the databases on which they rely, making the codes portable from system to system, and easing the difficulties involved in using the codes. During the last 5 years, special-purpose computer programs, based on the source codes of the principal codes, have proliferated (Parkhurst 1996). These special-purpose codes have databases tailored to the situation being studied.B. Calculation of Activity Coefficients. ‘The activity is “the tendency of a species to react” (Campbell 1970). It is substances’ a ies, that are used to calculate equilibrium constants and solubility products. The solubility products are keys, to predicting precipitation of solids from solution and dissolving the solids into solution. ‘The thermodynamic activity of a substance i ina solution is a, Use of an activity coefficient allows calculation of the activity of this component from its concentration, = 16 (vet) Activity coefficients approach one at high dilution of a solution. At high dilution, the behavior of a solution approaches “ideal” solution behavior. ‘The first truly successful approach to calculating activity coefficients for species in ionic solutions was proposed by Debye and Hiickel (1923). Their approach has been widely used and extended since its introduction. Glasstone (1946) and Lewis and Randall (1961) give good descriptions of the theory and its applications. More sophisticated treatments are also available (e.g., Mazo and Mou 1979). While valid at low to perhaps moderate concentrations, the Debye-Hickel approach fails at high concentrations. Recent coding efforts have incorporated virial equations developed by Pitzer for activity coefficients (e.g., Pitzer 1979, 1991; Clegg and Whitfield 1991). These allow more exact calculation of activity coefficients for solutions at high concentrations. . Uncertainties in Numerical Equilibrium Codes Fifteen years ago, Nordstrom et al. (1979) discussed uncertainties in the numerical codes then in use for calculating chemical equilibria in aqueous systems. Their comments remain valid today: “The use of activity coefficients to describe the non-ideal behavior of aqueous electrolytes reflects ur uncertain knowledge of ionic interactions and as a consequence we must approximate activity coefficients with semi-empirical equations.” ‘it is quite common for solubility product constants and complex stability constants to vary by 1 to 3 orders of magnitude (in different models)...Quite clearly this amount of uncertainty can cause large differences in the computer results and probably contributes the largest single source of error...the lack of carefully evaluated thermodynamic data will continue to be the most serious limitation for any type of chemical modeling. “(There is an) inconsistency and inadequacy of activity coefficient equations.” “Another related problem is the calculation of activity coefficients for neutral complexes. Very little reliable information is, available on the activity of neutral ion pairs and since these often comprise the dominant species in aqueous systems their activity coefficients can be an important source of uncertainty." “The fourth limitation is the assumption made about the redox state of aqueous systems. The distribution of redox species depends on what redox potential is assumed to dominate the chemical equilibrium... mposed redox equilibria may not represent a realistic distrib n of species.”What Daveler and Wolery (1992) say of the £Q3/6 codes is true of all numerical equilibrium codes. “What one can do with EQ3NR or EQ6 depends to a high degree on what is on the supporting data file and if so how the species and reactions on the data file are organized. For example, iron does not appear on the hmw data file, so this file can not be used to model the behavior of iron in brine- mineral systems. Similarly, uranium does not appear on the sup data file. Even if a chemical element does appear on a given data file, the corresponding species required for a given problem must also appear on it.” A cautionary note by Wolery (1992a) is worth repeating. "Geochemical modeling codes are not black boxes. Much of the usefulness (or lack of) that comes from their use is determined by the level of knowledge brought to bear by the user....Any results obtained by modeling calculations should be weighed against descriptive knowledge of the system being modeled." Since the time of the earlier comments, the quality and extent of thermodynamic data in the code databases has improved. Little else has changed. These uncertainties should motivate caution and restraint in interpreting results of numerical modeling of chemical equilibria in aqueous systems. V. THE EQ3/6 THERMODYNAMICS SPECIATION CODES A. Attributes of the EQ3/6 Codes. It is mentioned above in Section IV.A that many numerical equilibrium codes have been developed over the past 30 years. Among these is the EQ3/6 set of codes, originally created by T. J. Wolery (1978). The characteristics of some of the more popular codes are compared in Table 1, adapted from a similar table in Mangold and Tsang (1991). This table shows that the EQ3/6 codes encompass more possible precipitated mineral types than any of the other codes. While the data underlying Table 1 is 6-7 years old, the proliferation of codes mentioned above in Section IV.A makes a realistic updating of this table impossible. A current sampling of other codes indicates that the EQ3/6 codes still consider more precipitated mineral types than any other popular code. ‘Another property of the EQ3/6 codes is the ability to calculate along a reaction path, and to stop anywhere between the starting point and final equilibrium. Few codes have this capability. ‘The EQ3/6 codes have undergone continuous improvement since their origin. The version used for this report's calculations was 7.2 and is usable on 386 and 486 MS-DOS personal computers. Since the Mangold-Tsang table was developed, the EQ3/6 capabilities have expanded. The number of elements considered has increased from 47 to 78, the number of aqueous species from 686 to 851, of ‘minerals from 713 to 885, and of gases from 11 to 75 (Daveler and Wolery 1992). While other codes have also improved their capabilities, EQ3/6 apparently remains the one with the highest numbers of mineral types and thus is appropriate for studying precipitation behavior.B. Codes and Files in the EQ3/6 System. Several documents thoroughly describe the EQ3/6 codes and give detailed descriptions of their bases (Daveler and Wolery 1992, Wolery 1982a and 1992b, Wolery and Daveler 1992). Wolery (1979) ‘and Wolery et al. (1990) give shorter descriptions of the EQ3/6 codes, These sources may be consulted for details about the codes. Only aspects pertinent to the present work are mentioned in the next paragraphs. ‘The EQ3/6 software system presently consists of 3 computer codes and 19 files. The 3 codes are titled EQPT, EQ3NR, and EQ6, Of the files, the titles of § begin with dataO, 5 with datat, and the rest have titles indicating their purpose, e.9., input, output, etc. While this study used the 3 codes, it did not use all the files. Figure 1, adapted from Wolery (1992a), shows the flow of information among the 34 EQUILIB 26 E036 aT MINTEQ PHREEQE SOILCHEM ‘TRANSCHEM WATEQAF Aqueous Orga- Gases Species nics >520 200 686 Redox Ele- ments >38 (@) Adapted from a table presented by Mangold and Tsang (1981). Precip./ Dissoin. Minerals >340 186 13 Activity Coeff. Davies &DH DH D-H, Davies & Pitzer DHE Davies Davies, neutral species & Pitzer Davies &DH Bromley- Zem: & Pitzer Truesdell- Jones, DHE Davies24 Table 2, MAJOR CHARACTERISTICS OF THE EQ3/6 DATA FILES” Fite Name com sup nea pit hmw (Suffix) GEMBOCHS SUPCRT92" NEAdraft Pitzer Harvie, Source (LLNy” report? (1979) Maller, & Weare Extended Extended Extended =—~Pitzer’s. Pitzers Coefficient Debye- Debye- Debye- Equations Equations Relationship Hilcket Hoke! Hckel Temperature 0.300% 0-300%C 0-200°C o-100° 25°C Limits Number of Chemical 78 69 32 52 9 Elements Number of Basis 147 4105 50 62 8 Species Number of ‘Aqueous 852 315 158 68 7 Species Number of Pure 886 130 188 381 st Minerals Number of Solid 12 0 0 ° 0 Solutions Number of Gas 78 16 76 38 3 Species, (@) Adapted from a table in Wolery (19922). (©) GEMBOCHS is a software code developed at Lawrence Livermore National Laboratory. (©) The sup data file is based entirely on SUPCRTS2 (Johnson, Oclkers, and Helgeson 1982). (@ The nea data file is based on a database developed as part of the Thermochemical Data Base project of the Nuclear Energy Agency of the Organization for Economic Cooperation and Development. The first volume of a projected series reporting these data has appeared (Wanner and Forest 1992).25 Table 3. RESULTS FROM SOLVING PRECIPITATION PROBLEM #1— PRECIPITATION OF PORTLANDITE FROM A CONCENTRATED SOLUTION Database Ideal Ideal com, coM, PIT HMW Soin. #1 Soin. #2" Davies B-dot ‘The Precipitate: ‘Amt. Ca(OH), 463 463 45.43, 45.44 45.91 44.93, Ppt, g/L Kea! 0.98 0.98 0.99 0.97 Th pH 112 13 114 7 18 118 [cat], 1.628 1.628 0.624 1.450 1.633, 1.647 mol. for, 0.0017 0.0018 0.0026 0.0055 0.0119 0.0381 moll. oan 1.000 4.000 2.653, 0.347 2.255 2211 ‘or 1.000 41.000 0.566 0.550 0.0842 0.0348 PKepicaora 5.44 5.46 5.44 5.19 fr cones. & y5 PK catty) 5.33 5.28 521° 521° 521° 5.19 (fr. databases) (@) Using solubility products from Lide (1993). {b) Using solubility products from Dean (1992). (©) Calculated from standard free energies of formation in database.26 Table 4, RESULTS FROM SOLVING PRECIPITATION PROBLEM #2~ POSSIBLE PRECIPITATION OF PORTLANDITE, Database Ideal Ideal com, com, PIT HMw Soin. #1 — Soin, #2” Davies B-dot The Precipitate ‘Amt. Ca(OH), 0.350 0.310 0.0 00 0.348 0.0 Pot. g/t. Xen ° ° 0.99 ° The pH 124 122 123 122 128 128 (ca), 0.0193 0.0195 0.0133 o.o189 0.0193 0.0240 molt (oH), 0.0186 0.0168 0.0228 0.0284 0.0397 0.041 molt. toms 4.000 4.000 1.08 0.234 0.594 0.492 tos 1.000 1.000 0.580 0284 0.451 0.423 PKecoin © © 5.44 © (fr. cones. & y's) PK oaonia 5.33 5.26 521 521% 521 sag (fr. databases) (@) Using solubility products from Lide (1993). (©) Using solubility products from Dean (1992) (©) Solubility products cannot be calculated from solute concentrations and activity coefficients because ‘ho precipitation occurs. (@ Calculated from standard free energies of formation in database.ar Table 5. RESULTS FROM SOLVING PRECIPITATION PROBLEM #3— SIMULTANEOUS PRECIPITATION OF GYPSUM AND PORTLANDITE Database Ideal Ideal com, com, PIT Soin. #1 — Soin. #2” Davies Bedot The Precipitate ‘Amt. Ca(OH) Pot, of Amt. gypsum ot. of Xeat Rite Yeo Vea The liquid pH 128 134 122 Ica’), 0.00123 0.00036 0.0137 molt. [OH], 0.061 0.124 0.0242 move [so], 0.058 0.028 0.00867 mol You 1.000 4.000 1.37 1.000 1,000 0.576 1.000 1,000 0.255 PKexicacrs2} (fr. cones. & 7's) PKexicarracs (fr. databases) PK spicaso (fr. cones, & y's) PKssicaso«) 4.15 5.04 (fe. databases) (@) Using solubility products from Lide (1993) (©) Using solubility products from Dean (1992). (©) Calculated from standard free energies of formation in database.28 Table 6. RESULTS FROM SOLVING PRECIPITATION PROBLEM #4— EVAPORATION OF WATER FROM SUPERNATANT SOLUTIONS RESULTING FROM PROBLEM #2 Amounts of precipitates and water are per liter of original solution. Database Ideal com, com, PIT Soin, Davies B-dot ‘The Precipitate: Portlandite {Ca(OH}. 9 Halite [Nac], 9 Thenardite [NaSOu, Glauberite [Na,Ca(SO.)2], 9 The liqui 13.2 13.2 13.6 137 45.2 452 452 452 475 7.19 6.99 6.97 0.00017 0.00287 0.00087 0.00146 4.33 6.49 5.87 5.44 0.0574 0.0860 0.0955 0.142 0.00331 0.0799 0.665 0.697 341 1.55 1.86 1.84 21.82 0.654 3.55 0.548 0.533 0.533 0.548 0.533 0.411 0.562 0.0498 0.0043829 Table 6 (cont.) Database Ideal coM, CoM, PIT HMw Soin, Davies Bedot ‘The liquid (cont, PK caona 5.44 5.44 544 5.19 (fr. cones. & 7's) PKepicaorna) 5.21% 5.21% 521° 5.21% 5.19 (fr. databases) PK e209 “1.59 1.59 1.59 187 (fr. cones, & 7's) PKeseacy “1.59 “159° 1.59 1.59 “1.57 (fr. databases) PKerpis28041 031 0.31 0.31 0.29 (fr. cones. & y's) PKepia2s0 0.31 ost 0.31 0.31 020° (fr. databases) PK spqiancarso42) 5.47 5.AT 5.47 5.25 (fr. concs. & y's) PKepqs2cas092] SAT 5.47 5.479 547° 5.240 (fr. databases) (@) Using solubility products from the COM database. (©) This value assumed to match results of EQ3/6 runs. (©) Calculated from standard free energies of formation in database.30 ‘Table 7, MASS BALANCES All quantities are in moles. Total amounts calculated to be entering or leaving are underiined. In theory, the amount of a particular ion entering should agree with the sum of the amounts of that ion leaving, Database com, com, PIT HMw Davies Bedot Precipitation Problem #1 Portlandite Precipitation Calcium Balance: Ca" in entering CaCl solution 4.505 4.505 4.505 4.505 Calcium in precipitated Ca(OH), 1.226 1.227 1.239 1.213 Ca" ion in final solution 1.248 2.300 3.267 3.293 CaCt’ in final solution 0.552 0.305 Cach(aq) 1.439 0.640 CaOH in final solution 0.044 0.034 Total calcium in final forms 4.508 4.506 4.508 4.508 Precipitation Problem #2 Possible Portlandite Precipitation Calcium Balance: Ca’* in entering CaCl, solution 9.07208 = 0.07208 9.07208 0,.07208 Calcium in precipitated Ca(OH)2 0.01410 Ca" ion in final solution 0.03078 0.05680 0.05799 0,.07206 Cac’ in final solution 0.00920 0.00515 cacifaq) 0.01687 0.00601 CaOH' in final solution 0.00644 = 0.00413 Total calcium in final forms 0.07209 © 0.07209 9.07209 0.07208a4 Table 7 (cont.) Database CoM, com, PIT HMW Davies Bedot Precipitation Problem #3 ‘Simultaneous Portlandite and Gypsum Precipitation Calcium Balance: Ca" in entering CaCl, solution 4.505 4.505 4.505 4.505 Calcium in precipitated Ca(OH)2 1.470 1.165 1.208 1.186 Calcium in precipitated CaSO,-2H,0 3.239 3.189 3.208 3.218 Ca" ion in final solution 0.044 0.133 0.0943 0.1082 CaCr in final solution 0.012 0.013 CaCh(aq) 0.024 0.016 ‘CaOH in final solution 0.008 0.011 Calcium in CaSO,(aq) 0.016 0.016 Total calcium in final forms 4.510 4513 4510 Sulfur Balance: ‘Sulfur in entering Na,SO, solution 3.520 3.520 3.520 3.520 Sulfur in precipitated CaSO,2H,0 3.239 3.159 3.208 3.218 Sulfur in SO 0.026 0.121 0.323 0.313 Sulfur in NaS” 0.249 0.237 Sulfur in CaSO«(aq) 0.016 0.016 Total sulfur in final forms 3.530 3.533 32 3.53132 Table 7 (cont) Database com, com, PIT HMw Davies B-dot Precipitation Problem #4 Evaporation of Water Calcium Balance: Calcium in entering solution 0.03363 0.04434 0.03143 0.03544 Calcium in precipitated Ca(OH). 0.01985 0.01498 0.01344 0.01952 Calcium in precipitated Na,Ca(SO,)2 0.01368 0.02893 0.01796 0.01582 Ca" ion in final solution ©.00001 0.00022 0.00004 0.00009 CaCl,(aq) in final solution 0.00038 0.00040 ‘CaSO,(aq) in final solution 0.00007 0.00007 Cac in final soluti 0.00004 0.00008 CaOH' in final solution 0.00004 0.00008 Total calcium in final forms 0.03385 0.04472 0.03144 0.03543 Sodium Balance: ‘Sodium in entering solution 33087 3.3054 «= 3.3074 3.9070 ‘Sodium in precipitated NaCl 26378 2.5218 = 2.8717 2.8779 ‘Sodium in precipitated Na;Ca(SO.)2 0.0274 = 0.0578 0.0359 (0,.0318 Sodium in precipitated NazSO, 0.1062 0.0740 0.0838 0.0824 Na’ in final solution 03649 © 0.6011 = 0.4502 0.4482 NaCl(aq) in final solution 0.4939 0.5380 NaSO; in final solution 0.0280 0.0386 NaOH(aq) in final solution 0.0259 0.0282 Total sodium in final forms 36841 = «3.8506 3.4416 3.4401Database Precipitation Problem #4 Evaporation of Water (cont.) Sulfur Balance: Sulfur in entering solution Sulfur in precipitated Na;Ca(SO,)2 Sulfur in precipitated Na,SO, SO," ion in final solution NaSO¢ in final solution ‘CaSO,(aq) in final solution Total sulfur in final forms Chlorine Balance: Chiorine in entering solution Chlorine in precipitated NaCl Cf ion in final solution NaCi(aq) in final solution 2x CaCl,(aq) in final solution Cact in final solution Total chlorine in final forms 33 Table 7 (cont,) com, Davies 9.09711 0.01368 0.05309 0.00025 0.02797 0.00007 0.09507 3.1246 2.6378 0.3321 0.4939 0.0007 0.00004 3.4646 com, B-dot 0.11934 0.02893 0.03699 0.00668 0.03858 0.00007 o.11t24 3.1063 2.5218 0.5426 0.5360 0.0008 0.00007 3.6032 PIT 0.10788 0.01798 0.04190 0.04283 HMW 10433 0.01882 0.04118 0.04481 0.10182 2.8779 0.3497AA Appendix A PROBLEM STATEMENTS OF FOUR SIMPLE PRECIPITATION PROBLEMS AND SAMPLE PROBLEM CALCULATIONS FOR IDEAL SOLUTIONS Precipitation Problem #1 Precipitation of Calcium Hydroxide (Portlandite) by Mixing of Concentrated Solutions of Calcium Chloride and Sodium Hydroxide Problem Statement. One liter of a water solution containing 500 g dissolved CaCl, is mixed at 25°C with one liter of a water solution containing 100 g dissolved NaOH. How much Ca(OH), precipitates? ‘What are the species remaining in solution, and how much is there of each species? Data. Atomic Weights: Ca: 40.08 ck 35.453 4H: 1.0079 Na: 22.9897 ©: 15.9904 Molecular Weights: CaCl, 110.99 NaOH: — 40,00 Ca(OH)a: 74.09 Solubility Product of Ca(OH)2: 4.68 x 10° [From Lide (1993). Solution #1—Using Solubility Product and Assuming an Ideal Solution. Total volume of solution: 2 titers. Initial molar amounts: 500/110.99 = 4.505 moles CaCl 100/40.00 = 2.500 moles NaOH. Molar concentrations: Sodium ion: 2.500/2.000 = 1.250 molesiliter Na’. Chloride ion: (4,505)(2)/2,000 = 4.505 molesiliter Cr. Solubility of Ca(OH): in water: Reaction: Ca‘ + 20H’ Solubility product relationship: [Ca"“]]OHT’ = 4.68 x 10°, Let x be the gram-equivalents of Ca’ that precipitate from one titer of solution as Ca(OH)2. Then the amounts remaining in solution are: [OH] = [OHJp- 2x; {[OH} = 1.250 molestlter} {ca 2.253 molesilter}, From the solubility product relationship: {{Ca"’Jo- XH[OH]o - 2x)? = 4.68 x 10° Since 2x = [OHJp, x ~ 0.625 molesilter [Ca"*] = 2.253 - 0.625 = 1.628 molesfiter [OHY ~ 468 x 10°/1.628 [OH] ~ 1.696 x 10° molesiiiter The pH of the solution is -log{(10")/(1.696 x 10°)] = 11.2A2 ‘An iteration of the solution procedure, using the new value of [OH], gives a corrected value of [OH] of 1,695 x 10° molesiliter. The first solution is close enough. ‘An ion balance on the process: The mixed solution had 2.50 moles Na" ions and 2.50 moles OH’ ions from the sodium hydroxide solution. ‘The mixed solution had 4.505 moles Ca"" ions and 9.010 CT ions, from the calcium chloride solution. Essentially all the hydroxyl ions and 1.25 moles of Ca" ion precipitated, leaving 3.26 moles Ca" ion in the solution. The 3.26 Ca plus the 2.50 moles Na‘ ion balance the 9.01 moles CI in the solution. ‘Amount of calcium hydroxide precipitating: 1,25 moles of Ca"” precipitates, which means that 1.25 moles of Ca(OH)2 precipitates. 1.25 x 74.09 = 92.6 g of calcium hydroxide precipitates. Precipitation Problem #2 Possible Precipitation of Calcium Hydroxide from Mixing Dilute Solutions of Calcium Chloride and Sodium Hydroxide with a Concentrated Sodium Chloride Solution Problem Statement. One-liter batches of three solutions are mixed together at 25°C. One liter of a water solution containing 8 g dissolved CaCl, one liter of a water solution containing 3 g dissolved NaOH, and one liter of a water solution containing 500 g dissolved NaCI are mixed together. How much CaSO, precipitates? What are the species remaining in solution, and how much is there of each species? Data. Atomic Weights: Ca: 40.08 ck: 95.453 H: 1.0079 Na: 22.9897 oO 15.9994 Molecular Weights: CaCl: 110.99 NaOH; 40.00 Nacl: 58.45 Ca(OH)2: 74.09 ‘Solubility Product of Ca(OH)»: 4.68 x 10° [From Lide (1993)] Solution #1--Using Solubility Product and Assuming an Ideal Solution, Total volume of solution: 3 liters. Initial molar amounts: 8/110.99 = 0.07208 moles CaCh, 3/40.00 = 0.07500 moles NaOH. 500/58.45 = 8,554 moles NaCl. Initial molar concentrations: Sodium ion: (0.075+8.554)/3.000 = 2.876 molesfliter Na" Chloride ion: (0.0721+8.554)/3.000 = 2.875 molesilter CI. Hydroxyl ion: 0.0750/3 = 0.02500 molestliter OH. Calcium ion: 0,07208/3 = 0.02403 molesfiter Ca’*. Solubility of Ca(OH), in CaCl-NaOH-NaCl solution: Reaction: Ca" + 20H Solubility product relationship: [Ca""OH = 4.68 x 10°. Let x be the gram-equivalents of Ca’ that precipitate from one liter of solution as Ca(OH)AS Then the amounts remaining in solution are: [OH] = [OH] - 2x; {[OH]o = 0.02500 molester} [ea"'}= [Ca x; {{Ca"].= 0.02403 molestiter} From the solubility product relationship: {[Ca"*Jo- xH{[OH]p - 2x)? = 4.68 x 10° ‘The approximation made in Problem #1 is not possible here. Solving this cubic equation by trial-and- error yields (00472 moles/iter 0.02403 - 0.00472 = 0.01931 molesiliter {OH] = 0.02500 - (2)(0.00472) = 0.01556 motesfiter The pH of the solution is -log[(10™)/(0.01556)] = 12.1 ‘Amount of calcium hydroxide precipitating: 0.00472 mol/L of Ca" precipitates, which means that 0.00472 mol/L of Ca(OH), precipitates. 0.00472 x 74.09 = 0.350 g/L of calcium hydroxide precipitates, ‘oF a total of 1.049 g of calcium hydroxide precipitates from the 3 liters of solution Precipitation Problem #3 Simultaneous Precipitation of Calcium Sulfate (Gypsum) and Calcium Hydroxide (Portlandite) by Mixing of Solutions of Calcium Chloride, Sodium Sulfate, and Sodium Hydroxide Problem Statement. One-liter batches of three solutions are mixed together at 25°C. One liter of a water solution containing 500 g dissolved CaCl, one liter of a water solution containing 100 g dissolved NaOH, and one liter of a water solution containing 500 g dissolved Na,SO, are mixed together. How much Ca(OH) precipitates and how much CaSO, precipitates? What are the species rem solution, and how much is there of each species? Data. Atomic Weights: Ca: 40.08 ch 35.453 H: 1.0079 Na: 22.9897 oO: 15,9994 s: 32.066 Molecular Weights: CaCk: 110.99 NaOH: 40.00 NaySOx 142.06 Ca(OH)»: 74.09 CaSO, 136.14 Solubility Product of Ca(OH): 4.68 x 10° [From Lide (1993)] Solubility Product of CaSO,: 7.1 x 10° [From Lide (1993). Solution #1—Using Solubility Products and Assuming an Ideal Solution. Total volume of solution: 3 liters. Initial motar amounts: 500/110.99 = 4.505 moles CaCl. 100/40.00 = 2.500 moles NaOH. '500/142,06 = 3.520 moles NaxSO,Ad Initial molar concentrations (before precipitation): Calcium ion, [Ca""Jo: 4.505/3.000 = 1.502 molesfiter Ca”. Sodium fon, [Na"Js: [2.500+(2)(3.520)/3.000 = 3.180 moles -r Na’ Chloride ion, [CI]Jo: 9.010/3,000 = 3.003 molesfliter Cr. Hydroxyl ion, [OHJo: 2.500/3.000 = 0.833 molesiliter OH Sulfate ion, [SOx]: 3.520/3.000 = 1.173 molestliter SO,” ‘Solubility of Ca(OH). in water: Reaction: Ca + 20H Solubility product relationship: [Ca""J[OH 4.68 x 10° Solubility of CaSO, in water: Reaction: Ca"’ + SO; <> CaSO, Solubility product relationship: [Ca™"[SOq] = 7.1 x 10°, Let x be the gram-equivalents of Ca” that precipitate from on of solution as Ca(OH). Let y be the gram-equivalents of Ca" that precipitate from on of solution as CaSOx. ‘Then the amounts remaining in solution are: [SOc] = [SOs }- y. From the solubility product relationships: {[Ca"*Jo - x- yHIOH} - 2x}* = 4.68 x 10° and {ICa"*o- x- yHISOo- y}= 7.1 x 10° Now, since there is an excess of sulfate and hydroxyl ions over that necessary to precipitate all the calcium ions, it may be assumed that x+y = 1.502 The first factor on the LHS of the first two equations is very small, and best set equal to [Ca""]. Thus there are three equations and three unknowns, x, y, and [Ca]. Solving the three equations simultaneously yiolds [Ca] = 1.248 x 10° molesiliter. For a better value of the quantity x + y, take 1.502-1.248 x 10° = 1.501. Solving the three equations. again simultaneously yields .386 molesiliter of Ca‘ precipitated as Ca(OH). y= 1.115 molesiiter of Ca" precipitated as CaSO,. [OH] = 0.839 - (2)(0.986) = 0.061 molesfiter. [SOu] = 1.173 - 1.115 = 0.058 molesiiter. [OH] is 0.061 M. The pH of the solution is -log[(10/0.061] = 12.8. ‘An ion balance on the process: The mixed solution had 12.50 moles Na® ions and 12.50 moles OH ions from the sodium hydroxide solution. The mixed solution had 4.505 moles Ca’ ions and 9.010 Cr ions from the calcium chloride solution. Essentially all the calcium and 9.010 moles of CH" ion precipitated, leaving 3.49 moles OH ion in the solution. The 9.010 CI plus the 3.49 moles OH ion balance the 12.0 moles Na’ in the solution. ‘The solution gives 0.386 mol/L of Ca" precipitating as Ca(OH), which means that (0.386)(74.09) = 28.6 G/L Ca(OH), precipitates, or (3)(28.6) = 85.8 g total Ca(OH), precipitates from the liter mixture. The solution also gives 1.11 moles/iter of Ca" precipitating as CaSO,, which means that (1.115)(136.14) = 151.8 g/L CaSO, precipitates, or (151.8)(3) = 455.4 g of CaSO, precipitates from the Siter mixture. Since the CaSO, precipitates from a water solution, it wll appear as the hydrate gypsum (CaSO.-2H,0), and the amount will be (151.8)(172.17/134.16) = 192.0 g/L gypsum precipitatingPrecipitation Problem #4 Evaporation of Supernatant Solution Remaining From Simultaneous Precipitation of Calcium Hydroxide and Calcium Sulfate Problem Statement. The supematant solutions remaining from the precipitations in Precipitation Problem #3 are evaporated almost to dryness. What substances precipitate in each case, and how much of each substance precipitates? What are the properties and compositions of any liquids remaining? Data. Atomic Weights: Ca: cl: H: Na: oO: s: Molecular Weights: CaCl; Ca(OH): CaSoy Nac: NaOH: NaSOu. Na,Ca(SO.)2 Solubility Products: Ca(OH): Nac: NaSOx! NazCa(S0_: {all from the COM database) 40.08 35.453 1.0079 22,9897 15.9994 32.066 110.99 74.09 136.14 58.443 49.000 142,043, 278.18 6.19x 10° 385 0.491 3.40 x 10° Solution #1—Using Solubility Products and Assuming an Ideal Solution. When £Q3/6 was used to evaporate the water, the initial solution was one liter, and the final product solutions all contained 45.2 g of water. Assume the same amounts for the ideal calculations. Thus, the original 3 liters of solution will become 1 Iiter for this calculation, Initial motar amounts: Na’: from Problem #8 Initial molar concentrations: Equations: (2.500+3.520°2)/3 = 3.180 moles Na" cr: (4.505°2)/3 = 3.003 moles CI Ca": 0.00123 moles Ca’ oH 0.061 moles OH SOs: 0.058 moles SO, INa"}o: [Cle: {ca (OH: [SO.Jo: 3.180/0,0452 = 70.35 mol/L. 3,003/0.0452 = 66.44 0,00123/0,0452 = 0.0272 0.061/0.0482 = 1.35, 0.058/0,0452 = 1.28 INa‘IICr] = 38.5 INa'P{S0¢] = 0.491AS [Ca JOHT = 6.19 x 10° [Na’F[Ca ISO, F = 3.40 x 10° Unknowns: w= mol/L of Na" going to NaCl x = mol/L of Na° going to NazSO« y = MoU of Na going to Na,Ca(SO.)2 z= mol/L of Ca"* going to Ca(OH)» Resulting equations: ((Na*]o-w-x-y)((Cl]o-w) = 38.5 (Na"Jowx-y) 7SOe}-%) = 0.491 (Na Jow-x-y) (Ca Jory-2) (1504 Jr)? = 3.40 x 10° ((Ca"*-%y-2)((OH Jo-22)? = 6.19 x 10° Solution of system of equations: The system consists of four nonlinear algebraic equations containing four unknowns. The general approach to a system of this type involves one or more iterative optimization methods. In the present situation, however, an ad hoc approach is possible because of the characteristics of the problem. The unknown w is probably much larger than x or y or even x+y. ‘This means that the first equation may be solved for an approximate value of w by ignoring the presence of x and y. Then, knowing an approximate value of ([Na’].-w-x-), the second equation may be solved for x. This may be substituted back into the first equation, which may then be solved for an improved value of w. This operation may be cycled until the best possible approximations of w and x are obtained. Then, with good approximate values of (Na"]xw-xy) and (SO.]ox), the third equation may be solved for an approximate value of the quantity ({Ca’"I-V/y-z). Having an approximate value of (Ca"*J>-%y-z) enables the fourth equation to be solved for z. The term ([Ca‘'k-Yy-2) then may be solved for an approximate value of y. The entire operation is repeated, using the approximate values of x and y to obtain improved values of w, x, y, and z. This cycle is repeated until no change takes place in the values of the unknowns and the equations are satisfied. During the cycles, mass constraints (e.g., ¥ < 2[Ca""Jo,z < [Ca""Jo) were placed on sore of the variables. Following this procedure yields the following values: 1.415 mol x= 1.272 y= 0.00180 z= 0.0263 This leads to the following amounts precipitating: Portlandite: (0.0263)(74.09)(0.0452) = 0.0881 g Halite: (61.415)(88.443)(0.0452) = 162.2 Thenardite: (1.272)(142.043)(0.0452)/2 = 4.08 Glauberite: (0.0263)(278.18)(0.0452)/2 = 0.165 ‘and to the following amounts in solution: INa’} 70.35 - (61.415+1.272+0.0018) = 7.66 mol/L {ca": 0.0272 - (%4*0.0018+0.0263) = 0.0 {cn 66.44 - 61.415 = 5.03 {OH} 1.35 - 2°0.0263 = 1.30 [so;1: 4.28 - (4°1.272+0.0018) = 0.642 ‘The amounts precipitating and the amounts in solution are recorded in Table 6.Ba Appendix B ‘SAMPLE CALCULATION OF SOLUBILITY PRODUCT FROM FREE ENERGIES OF FORMATION This appendix caloulates the solubility product of calcium sulfate from listed free energies of formation of calcium sulfate, the calcium ion, and the sulfate ion. The standard free energies of formation listed below are obtained from the EQ3/6 file datad.hmw. Species AG; Cas, -316.226 kcalimol ca’ -132.302 80, “AT7.974 Basic relationship: AG,, =-RT én K,, Reaction: CaSO, « Ca’ +0; AGien = AG cas} + AG sox— ~ AGjcasog AGieq = -177.974 - 132,302 + 816.226 = 5.950 kcal/mol én = -(6.950)(1000)/(1.987)(298.2)} = -10.04 tog = -10.04/2.3026 = -4.364 ‘The parameter pk.» is equal to the negative of the logarithm of the solubility product. The above calculation makes pk., equal to 4.361. This is extremely close to the value of 4.3621 listed in the file data0.hmw. It also may be compared with the value of 4.47 from the EQ3/6-HMW calculations reported in Table 4 for CaSOx,ct Appendix C MODELING MULTICOMPONENT PRECIPITATION FROM NONIDEAL SOLUTIONS Jn Problem #8, the amounts of gypsum and portlandite predicted to precipitate by ideal-solution calculations matched reasonably well the amounts predicted to precipitate by nonideal-solution calculations, This is reminiscent of the general chemistry truism that inclusion of nonideality in an equilibrium calculation often does not aiter the calculated equilibrium concentrations significantly (cf, €.9., Campbell 1970). {In the general chemistry truism, the cause is straightforward. Often, the activity coefficients in the ratio that composes the equilibrium constant approximately cancel. The same can be true of ‘multicomponent precipitation, as is shown below in the discussion following Table C-1 However, there is another possible cause for ideal-solution calculations to predict well the amounts precipitated from nonideal solutions when multiple substances precipitate. The following development shows there are combinations of solubility-product ratios and concentrations that will cause this to occur. It does not necessarily occur; particular combinations of solubilty-product ratios and concentrations are necessary. An approach is developed below that predicts when this effect will take place. The model solution has a cation C” and two anions At’ and AZ. The salts CA1 and CA2 are sparingly soluble, with solubility products Key: and K.,2. The cation C* is the limiting ion. Let x be the amount of A1 that is converted to At and y be the amount of A2 that is converted to CA2. Since the salts are sparingly soluble, almost all the cation C* will be precipitated, and xtysIC'h (ct) ‘An expression for x in terms of y may be obtained from a ratio of the solubility-product, relationships. For the ideal calculation of this situation, ICWOATI, ~ ies) _ Kop Kee (anh co (C1 QA2 Ty Yuu) Koga Koga MaxTA2”),~[C*] 0} ‘As seen, there is a limited range of Kepi/K sa in which Eq. (C-2) is valid. When the left-hand inequality is not satisfied, no CA2 precipitates, and the solubility product relationship is not valid for [C°)[A2. ‘When the right-hand inequality is not satisfied, no CA1 precipitates, and the solubility product relationship is not valid for [C"][A1]. The following development is valid only for the limited range of Eq. (C-2). Canceling where appropriate and solving for x yields [AI fp ~22 (A2"D ~ Yuu) Kepoc2 For a real or nonideal solution the analog of Eq. (C-2) is (rex) (C72) AP — Kea) _ Kops (res )ICT y50-) TAZ To Yeea) Kapa” Max(Ar 1.0) - Yas [a2], Yan Again, there is a limited range over which this equation is valid, and the following development applies only to this range. Solving Eq. (C-4) for x gives the analog of Eq, (C-3) for real or nonideal solutions: ot fark, ega Max{((A2"], ~ [C°],).0} cy Xs K, = IAT -[ae fe wor, cal) Cs b Ya | Koga * » ‘Solving Eq. (C-1) for y and substituting it into Eqs. (C-3) and (C-5) gives the implicit equations for Xcea! and Xai Kena (ACI — RE (A2"Tp~ [6° + Rea) cs) = and Kea “IATL [|e (AD ~ [CL + ea) en Tar | Keo ‘What are of interest here are the two ratios Xa/Xcen aNd Yres/Yisus- TO ease the algebra, let = Xea/Miea B YewlVaean and & = vachar.. Fitst consider a. In this simple situation, Eqs. (C-6) and (C-7) can be solved explicitly for Xdea) ANd Xe) and the ratio set equal to a. This approach yields TAU = eg Kuga) (AZ ~ 10") : Keel * Te Cop, Kea C8) ‘and TAT, = E(Kup Kaya) CA2"Ip = [0")) 1 FAT: = EK ps Kage) GA" = [C) ond 1+ 5p Koga) ~ Dividing Eq, (C-9) by Eq, (C-8) results in sem HAT ~SlKps Kuga MUA2"y 10° EYL + Cpa! Kegadl (erm MATL ~ Kops / KepoIA2 B ~ (CL) + E Keg / Kuga] Table C-1 presents the results of substituting various concrete values into Eq. (C-10). The first two sets of values show that « can differ significantly from one. in these two cases, a= 2 and a=0. ‘These situations represent the two extremes of the valid range of this development. In the first situation,« is atts maximum, just at the point where no CA2 precipitates. In the second, a. is at its minimum, just at the point where no CAt precipitates. Table C-1. EFFECTS ON Xa/Xiden AND da/dé|iee1 OF CONCENTRATION, SOLUBILITY- PRODUCT RATIO, AND ACTIVITY-COEFFICIENT RATIO FOR THE PRECIPITATION MODEL Cone, Cone. KegalKept eater. oa! Xideat daldEleo-s of At of AZ © @ 2IC"ly 2IC"lo 05 ZC} ACh 2 2IC"}o ¥IC'}o 05 2IC"b IC's 2 ‘The second two sets of values show that a can be very close to one, even when the ratio of activity coefficients (2) differs significantly from one. When &= 1, of course, effects of the activity coefficients cancel, the numerator and denominator of Eq. (C-10) are identical, and «= 1. Table C-1 shows that even when effects of the activity coefficients do not cancel, « can still be very close to one. This depends on the particular combination of ion concentrations and solubility-product ratio. Analysis creates a standard for judging whether a particular combination of ion concentrations and solubility product ratio can cause « to differ significantly from one. If a(@) is expanded in a Taylor series, then pre (dale eal. aoa rors ] Go) +... Let {= 1. Then solution of Eq. (C-10) for a gives aE) =1 (C12) This is equivalent to asking what happens if the effects of the activity coefficients cancel. The obvious answer is that a(¢=1) should equal one, which it does. Equation (C-11) then becomes Ger} fe | Pe 2 Solving Eq. (C-10) for da/dé, yieldso4 da { [+ Kops /Kogo)d | =| 5 IAP = Kor Kops) GAZ ~ICD)| [LHR a? X( LEK ag Kea M Kay Ky (AZ BE) HAI ~ EKopi / Kye (PAZ ~ U Kept Koyo) ) (c-14) Table C-1 also presents the values of da/dElym+ for the cases mentioned above. It shows that with one set of concentrations and solubility-product ratios, the value of do/dé|.o- = -1.5. With another set of concentrations and solublity-product ratios, the value of do/dél.n1 = -2x 10%. The former situation resulted in a significant change of a, and the latter an insignificant change of a. The values of dadz}ko-: of course represent the sensitivity of « toa change in &, and this is an indicator of when will change noticeably if & is significantly different from one. Ifthe second-order and higher terms in Ea. (C-13) are small, they may be ignored. When this ‘cours, Eq. (C-13) becomes, a 1+ GauldelodE) . (15) A quick look at the values of and the values of da/dzhje1 in Table C-1 shows that Eq, (C-16) is not valid for any of the situations posed in the table. It gives changes in a. from the ideal that are in the correct direction and in the correct range, but the differences reflected in the Table C-1 values for a are not predicted closely by Eq. (0-15). It appears that if Eq, (C-13) is to be used for predicting the proper value of «. for a particular situation, it cannot be truncated after the first term. The development for the ratio Yas/Yuea, OF f, follows the same path with the same qualitative resulfs. There are particular combinations of concentrations and solubility products thet give close to 41, and an expression may be derived that tells when this will occur.D4 Appendix D DERIVATION OF EQUATION (Vill-33) The derivation begins with Eq. (Vill-15) of Section VIIILB, Again let x be the amount of Ca’ ion that precipitates as Ca(OH)2 and y the amount of Ca’ jon that precipitates as CaSOw-2H,0. This time a relationship for y in terms of x will be obtained from the ratio of the solubility-product relationships, For the ideal calculations of Precipitation Problem #3, _ cuitlts) Kgtcasos) Canceling where appropriate and solving for y yields 1, ~ fotHs#04L OH 2a? oo) Yaseat = [SOx Kegeoworsa} For a real or nonideal solution the analog of Eq, (VIll-15) is (ear) 12” Hey o4¢ (OH ~2%ea)” _ Kesicaroroat = 5 wviet7) (ear NEE Kg9;- MISO I= Yroa) —Keyieason and solving Eq. (VIll-17) for y_gives the analog of Eq, (0-1) for real or nonideal solutions: K afoasou) (OH), -2%ceu)* (02 Teor | Kafcxor Since almost all the calcium ion is precipitated in both the ideal and real-solution calculations, the approximation x+ye[Ca" (vill-19) Is valid. Solving this approximation for x and substituting it into Eqs. (D-1) and (0-2) gives the implicit ns for Yeo * 1805" ~ —— (OH, ~ 2100"), +2950) © and You 1807"), ~ 254 Kestasou GH, 20a" +24)" O-4) Yeo Kspieatornay This derivation concems Yres/Yises!, OF B. Asin the derivation for a, let = VYso4-/YoH+ From Eqs. (D-3) and (D-4),D2 (SO; ], - (=) SHES GOH}, - 28") 2%] Be —— 5) sor}, -E SHC2S041. (OH, -21CA™*}, + 2¥iea)? Kepioacorna) ‘Substituting the RHS Of Yrex = BYisow fOF Yresi ON the RHS of Eq. (O-5)'s numerator gives = foscsou “ [SOF"} ~ e (OH, ~ 2[Ca"*}p +28 Yideas)” = K ica ea JOH], - 2[Ca"*}y + 2 idea | This development assumes that the ideal calculations have been carried out, and that the only ‘unknowns in the above equation are p and &, The equation is implicit in Band can be written BeBe) . O72 Expanding this in a Taylor series gives = 8G+ sleet ] ea : Bx BEo) (2 lk —%o) fea ] G- bo)’ +... 8) Let &=1. Then solution of Eq. (D-6) for 6 gives BE) © This is equivalent to asking what happens if the effects of the activity coefficients cancel. The obvious answer is that (E:=1) should equal one, which it does. Ifthe second-order and higher terms in Eq, (D-8) are small, they may be ignored. When this ‘occurs, Eq. (0-8) becomes et |e : Pele [2 | » (0-10) ‘The denominator of the RHS of Eg. (0-6) equals yes. Using this equality and taking derivatives of both sides of Eq. (0-6) yields(iseess GOH}, - 2108", + 28 Yana” |] Yam! | Kegon & z Feed (OH), -21Ca"*h +28 vn om K gowns Solving for dpld and setting & equal to 1 isthe next step. Setting & equalto 1 makes f equal to 1; the ratio of solubility products times the squared term on the RHS of Eq, (D-11) equals [SO."hb- Yes when B equals 1. Implementing this gives a (2) (SO3"Io~ Ves) ol, "Yan {1 Keen Kapur) (SOL = Yea) Substituting this expression into Eq. (0-10) gives petv|———__@4801"} — Yue) dig Yiseall + AK eyousouy / Keygcacorpey) (SOG lo — Yuead]3) This is Eq. (VIlI-33) in the text.RA REFERENCES Bassett, R. L., and D. C. 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