Thermochemistry of Salts 0703

BO AKADEMI
TEKNISKA FAKULTETEN Processkemiska Centret FACULTY OF TECHNOLOGY Process Chemistry Centre
REPORT 07-03
Thermochemistry and melting properties of alkali salt mixtures in black liquor conversion processes Daniel Lindberg
Academic Dissertation Laboratory of Inorganic Chemistry
Thermochemistry and melting properties of alkali salt mixtures in black liquor conversion processes Daniel Lindberg
Academic dissertation
bo Akademi University Faculty of Technology Process Chemistry Centre Laboratory of Inorganic Chemistry
Preface
Preface
The work described in this thesis was carried out at the Process Chemistry Centre at bo Akademi University from 2002 to 2007 and at CRCT, cole Polytechnique de Montral during a six month stay in 2004. Funding for the work has been received from several sources: Nordic Graduate School of Biofuel Science and Technology, part of the Nordic Energy Research, the Fondation de lcole Polytechnique de Montral, U.S. Borax Inc., Andritz Oy, Foster Wheeler Energia Oy, International Paper Inc., Kvaerner Power Oy, Oy Mets Botnia Ab, Vattenfall Utveckling AB and the National Technology Agency of Finland (TEKES). All financial support is gratefully acknowledged. Professor Rainer Backman has been the main supervisor of the work presented in this thesis. I wish to express my deepest gratitude to Rainer for giving me the opportunity to do research on interesting topics in the field of high-temperature inorganic chemistry. The endless hours we have spent discussing thermodynamics, chemistry, and science in general have always kept me inspired to push forward in my research. I especially appreciate that he has always been available to help and support me in my work. The thermodynamic modeling presented in publications III-VI was performed together with Professor Patrice Chartrand at CRCT, cole Polytechnique, in Montral, Canada. The modeling work was planned in cooperation with Professor Chartrand, and he functioned as my supervisor during my visits to Montral. I wish to thank Patrice for giving me the opportunity to visit CRCT, Montral and for his supervision during my stays there. Patrices dedication to my work has helped me tremendously, and for that I am greatly thankful. I also want to acknowledge all the people at CRCT for making my stays in Canada enjoyable. I want to express my gratitude to Professor Mikko Hupa for giving me the opportunity to do my doctoral studies at the Laboratory of Inorganic Chemistry. His competence and his positive attitude have been a source of inspiration and it has given me a great platform for my doctoral studies. Special thanks go to Mr. Linus Perander for performing the experimental work for Publication II, as well as being a co-author of the paper. In addition, Linus comments on
Preface Publications III-VI were valuable. His contribution to the doctoral study has been important, and his cooperation and friendship are greatly appreciated. I thank Dr. Saied Kochesfahani and Dr. Helen Rickards for their support on the borate autocausticizing work, and for their contributions as co-authors to Publication II. Dr. Nikolai DeMartini and Professor Chris Bale are acknowledged for their comments on publications related to the thesis, and in addition Mrs. Debby Repka for her comments on the thesis. Mr. Peter Backman performed the experimental work for Publications I and VI. I wish to thank him for his diligence and accuracy in the experimental work. I want to thank all my colleagues, both past and present, at the Laboratory of Inorganic Chemistry who have ensured that my doctoral studies have been a tremendously rewarding time. I especially want to acknowledge Dr. Mischa Theis and Mr. Johan Werkelin, with whom I have shared the joy and agony of making a doctoral thesis the last couple of years. Finally, I want to thank all my friends and my family, whose love and support have kept my spirits up high during the whole process of making a doctoral thesis. I am especially grateful to my parents, whose support and encouragement have made it possible for me to to pursue a career in the field of science.
bo, February 2007
Daniel Lindberg
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Abstract
Abstract
Alkali salt mixtures play an important role in the chemical processes in a kraft recovery boiler burning black liquor. The smelt, a liquid phase containing mainly Na2CO3 and Na2S, is the main chemical product from the recovery boiler and is utilized for producing the pulping chemicals. Several reactions occur in the smelt, such as the sulfur reduction, which is a reaction between the smelt and the char carbon. Alkali compounds, such as alkali chlorides and various sulfur-containing species, play an important role in the formation of deposits on heat exchanger surfaces in the boiler. Molten alkali salts can also cause corrosion problems in the boiler. The thermochemistry and melting properties of alkali salt mixtures involved in black liquor and biomass combustion have been studied by evaluating and optimizing the thermodynamic data for all known phases in the Na+,K+/CO32-,SO42-,S2-,S2O72-,Sx2-,Cl-, Va- system using experimental data as input. Additional experimental data for melting temperatures in the ternary NaCl-Na2CO3-Na2SO4 and KCl-K2CO3-K2SO4 systems were obtained by simultaneous differential thermal analysis and thermogravimetry and the results were used as input for the thermodynamic optimization. The thermodynamic properties of the liquid phase were modeled using the Modified Quasichemical Model in the Quadruplet Approximation, which is a thermodynamic model developed especially for molten salts. The obtained thermodynamic database reproduces the solid-liquid equilibrium of the binary, ternary and quaternary systems within the experimental uncertainties. The database of thermodynamic data for all phases can be used in Gibbs energy minimization software for calculating the phase equilibria and all thermodynamic properties of multicomponent alkaline salt mixtures. The alkali salts are of great importance for ash-related problems in biomass combustion and for processes in black liquor combustion. Predictions of the melting behavior of the alkali salts are useful for understanding the behavior of the smelt bed and the formation of harmful deposits in the kraft recovery boiler. Borate autocausticizing is a concept for reducing the lime consumption at pulp mills by adding boron to the pulping process. The amount of Na2CO3 that needs to be causticized for the production of white liquor can be reduced by the borate reactions in
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Abstract the kraft recovery boiler. The autocausticizing reactions mainly occur in the smelt or in burning black liquor droplets. The effects of chemical and physical variations on the borate autocausticizing reactions in mixtures of alkali carbonates and alkali borates were studied by simultaneous differential thermal analysis and thermogravimetry. The results showed that the borate autocausticizing reactions are reversible, and that high temperatures and low borate contents enhance the conversion of borates to the preferred orthoborate form. High potassium contents and high partial pressures of CO2 inhibit the autocausticizing reaction. High conversion of the autocausticizing reaction can be attained at the conditions prevalent in the char bed of a kraft recovery boiler. The experimental results can be used as input for future thermodynamic evaluations of borate-containing alkali salt systems involved in combustion of boron-containing black liquors.
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Svensk sammanfattning
Svensk sammanfattning
Alkalisaltblandningar spelar en viktig roll i de kemiska processerna i en sodapanna. Sodapannesmltan, som huvudsakligen bestr av Na2CO3 och Na2S, tappas ut ur sodapannan och anvnds till att producera vitlut. Flera viktiga kemiska reaktioner sker i smltan. Svavelreduktionen sker huvudsakligen genom en reaktion mellan smlta och koks. Alkalifreningar, till exempel alkaliklorider och olika alkali-svavel freningar, kan leda till uppkomsten av belggningar p vrmevxlarytor. Alkalisaltsmltor kan frorsaka korrosionsproblem i sodapannan. I denna studie har de termokemiska egenskaperna och smltbeteendet fr alkalisaltblandningar relevanta fr svartluts- och biomassefrbrnning underskts genom en evaluering av experimentella termodynamiska data och fasjmviktsdata fr alla knda faser i det kemiska systemet Na+,K+/CO32-,SO42-,S2-,S2O72-,Sx2-,Cl-,Va-. En termodynamisk optimering av de termodynamiska funktionerna fr dessa faser utfrdes p basen av evalueringen. Smlttemperaturerna fr de ternra systemen NaCl-Na2CO3Na2SO4 och KCl-K2CO3-K2SO4 undersktes med simultan differentiell termisk analys och termogravimetri och resultaten utnyttjades som ingngsdata fr den termodynamiska evalueringen. Smltfasens termodynamiska egenskaper modellerades med den modifierade kvasikemiska modellen, en termodynamisk modell utvecklad fr jonsmltor. Jmviktsberkningar med den erhllna termodynamiska databasen terger fastfasvtskefasjmvikten fr de underskta binra, ternra och kvaternra systemen inom den experimentella oskerheten. Databasen kan utnyttjas i program fr kemiska jmviktsberkningar baserade p minimering av Gibbs energi fr att bestmma fasjmvikter och termodynamiska egenskaper fr system av alkalisalter viktiga fr askrelaterade problem i biomass- och svartlutsfrbrnning. Smltbeteendet hos alkalisalter ger information om frhllanden i smltbdden och om hur skadliga belggningar uppkommer i sodapannan. Boratautokausticering r en metod mnad att reducera kalkfrbrukningen vid pappersmassabruk genom att tillstta grundmnet bor i massaprocessen. Mngden Na2CO3 som br kausticeras fr produktionen av vitlut kan minskas genom boratets
Svensk sammanfattning reaktioner i sodapannan. Autokausticeringsreaktionerna sker huvudsakligen i smltan eller i brinnande svartlutsdroppar. Effekten av olika kemiska komponenter och fysikaliska frhllanden p autokausticeringsreaktionerna i blandningar av alkalikarbonater och alkaliborater undersktes med simultan differentiell termisk analys och termogravimetri. Resultaten visade att boratautokausticeringsreaktionerna r reversibla och att hga temperaturer och lga boratkoncentrationer gynnar omvandlingen av boraterna till ortoborat, som r gynnsamt fr autokausticeringen. Hga kaliumkoncentrationer och hgt partialtryck av CO2 hmmar autokausticeringsreaktionen. En hg omvandlingsgrad av boraterna kan uppns vid frhllanden som rder i koksbdden i en sodapanna. De erhllna experimentella resultaten kan anvndas som ingngsdata fr framtida termodynamisk evalueringar av alkaliboratblandningars kemi vid anvndning av bor fr att befrmja autokausticering vid svartlutsfrbrnning.
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Table of contents
Table of contents
Preface.................................................................................................................................. i Abstract .............................................................................................................................. iii Svensk sammanfattning ...................................................................................................... v Table of contents............................................................................................................... vii List of publications ............................................................................................................. x 1. Introduction..................................................................................................................... 1 1.1 Objective of the study ............................................................................................... 4 2. Alkali salts in the recovery boiler ................................................................................... 5 3. Thermodynamic modeling of alkali salt mixtures involved in black liquor combustion 9 3.1 Overview of the properties of ionic compounds and solutions................................. 9 3.2 Thermodynamic equilibrium modeling .................................................................. 10 3.3 Optimization of phase diagrams and thermodynamic data..................................... 12 3.4 Thermodynamic models of ionic solutions............................................................. 13 3.4.1 Ideal solutions .................................................................................................. 13 3.4.2 Nonideal solutions ........................................................................................... 14 3.4.3 Sublattice models ............................................................................................. 16 3.4.4 Compound Energy Formalism......................................................................... 18 3.4.5 Modified Quasichemical Model in the Quadruplet Approximation ................ 19 3.4.6 Extrapolation of excess Gibbs energy in multicomponent solutions............... 25 3.5 Thermodynamic evaluation and optimization of the Na+, K+/CO32-, SO42-, S2-, S2O72-, Sx2-, Cl-, Va- system .......................................................................................... 27 3.5.1 The Na-K-S system.......................................................................................... 29 3.5.1.1 Na-S .......................................................................................................... 31 3.5.1.2 K-S ............................................................................................................ 33 3.5.1.3 Na-K.......................................................................................................... 33 3.5.1.4 Na2S-K2S................................................................................................... 34 3.5.1.5 Na2S-K2S-S ............................................................................................... 34 vii
Table of contents 3.5.2 The Na+,K+/CO32-,SO42-,Cl-,S2-,S2O72- system................................................. 36 3.5.2.1 Binary systems .......................................................................................... 36 3.5.2.2 Na2CO3-Na2SO4 ........................................................................................ 38 3.5.2.3 Na2CO3-Na2S ............................................................................................ 38 3.5.2.4 Na2SO4-Na2S............................................................................................. 38 3.5.2.5 Na2SO4-Na2S2O7 ....................................................................................... 39 3.5.2.6 NaCl-Na2SO4 ............................................................................................ 41 3.5.2.7 NaCl-Na2CO3 ............................................................................................ 41 3.5.2.8 NaCl-Na2S................................................................................................. 42 3.5.2.9 K2CO3-K2SO4 ........................................................................................... 43 3.5.2.10 K2CO3-K2S.............................................................................................. 44 3.5.2.11 K2SO4-K2S .............................................................................................. 45 3.5.2.12 K2SO4-K2S2O7......................................................................................... 46 3.5.2.13 KCl-K2SO4 .............................................................................................. 47 3.5.2.14 KCl-K2CO3 ............................................................................................. 47 3.5.2.15 Na2CO3-K2CO3 ....................................................................................... 49 3.5.2.16 Na2SO4-K2SO4 ........................................................................................ 50 3.5.2.17 Na2S2O7-K2S2O7 ..................................................................................... 50 3.5.2.18 NaCl-KCl ................................................................................................ 51 3.5.2.19 Ternary systems ...................................................................................... 52 3.5.2.20 Na2CO3-Na2SO4-Na2S ............................................................................ 53 3.5.2.21 NaCl-Na2CO3-Na2S ................................................................................ 54 3.5.2.22 NaCl-Na2CO3-Na2SO4 ............................................................................ 55 3.5.2.23 KCl-K2SO4-K2CO3 ................................................................................. 57 3.5.2.24 Na2SO4-K2SO4-Na2S2O7-K2S2O7............................................................ 59 3.5.2.25 Na2CO3-Na2SO4-K2CO3-K2SO4 ............................................................. 61 3.5.2.26 NaCl-Na2SO4-KCl-K2SO4 ...................................................................... 63 3.5.2.27 NaCl-Na2CO3-KCl-K2CO3 .................................................................... 64 viii
Table of contents 3.5.3.28 Multicomponent systems: NaCl-Na2SO4-Na2CO3-KCl-K2SO4-K2CO3 . 66 3.6 Discussion ............................................................................................................... 68 3.7 Conclusions............................................................................................................. 68 4. Alkali borates in the kraft recovery boiler .................................................................... 69 4.1 Definitions of nonconventional causticizing concepts ........................................... 70 4.2 Borate autocausticizing........................................................................................... 71 4.2.1 Partial borate autocausticizing ......................................................................... 74 4.3 Objective of the experimental study of borate autocausticizing............................. 76 4.4.1 Borates in the recovery boiler .......................................................................... 76 4.4.1.1 Alkali orthoborates.................................................................................... 78 4.4.1.2 Alkali diborates......................................................................................... 78 4.4.1.3 Alkali metaborates .................................................................................... 79 4.4.1.4 Molten alkali borates................................................................................. 79 4.5 Experimental setup.................................................................................................. 82 4.6 Results..................................................................................................................... 84 4.7 Discussion ............................................................................................................... 90 4.8 Conclusions............................................................................................................. 92 5. Conclusions and implications ....................................................................................... 93 References......................................................................................................................... 95 Appendix A: Thermodynamic data of pure compounds Appendix B: Thermodynamic functions of solid solutions Appendix C: Interaction parameters of the liquid phase
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List of publications
List of publications
I. Lindberg, D., Backman, R. (2004) Effect of temperature and boron contents on the autocausticizing reactions in sodium carbonate/borate mixtures. Industrial and Engineering Chemistry Research, 2004, 43, 6285-6291. Lindberg, D., Perander, L., Backman, R., Hupa, M., Kochesfahani, S., Rickards, H. (2005) Borate autocausticizing equilibria in recovery boiler smelt. Nordic Pulp and Paper Research Journal, 2005, 20(2), 232-236.
II.
III. Lindberg, D., Backman, R., Hupa, M., Chartrand, P. (2006) Thermodynamic evaluation and optimization of the (Na+K+S) system. The Journal of Chemical Thermodynamics, 2006, 38(7), 900-915. IV. Lindberg, D., Backman, R., Chartrand, P. (2006) Thermodynamic evaluation and optimization of the (Na2SO4+K2SO4+Na2S2O7+K2S2O7) system. The Journal of Chemical Thermodynamics, 2006, 38(12), 1568-1583 V. Lindberg, D., Backman, R., Chartrand, P. Thermodynamic evaluation and optimization of the (Na2CO3+Na2SO4+Na2S+K2CO3+K2SO4+K2S) system. The Journal of Chemical Thermodynamics, In Press
VI. Lindberg, D., Backman, R., Chartrand, P. Thermodynamic evaluation and optimization of the (NaCl+ Na2SO4+Na2CO3+KCl+K2SO4+K2CO3) system. The Journal of Chemical Thermodynamics, In Press
Chapter 1- Introduction 1. Introduction

The kraft pulping process is the main chemical pulping process in the world today. In contrast to the mechanical pulping processes, chemical pulping processes separate the cellulose from wood chips by chemical means,. In the kraft pulping process, the wood chips are cooked in an alkaline solution containing dissolved Na2S and NaOH. Lignin and some carbohydrate material are dissolved from the wood chips during cooking. The resulting pulp, which is made up mainly of wood fibers, is separated from the cooking solution and used for the production of different pulp and paper products. The spent cooking solution, which is called black liquor, contains the dissolved organic matter, the inorganic material from the wood, and the spent cooking chemicals. The processing of the black liquor is an integral part of pulp mill operations. Much of the water has to be evaporated from the black liquor so that it can be burned. The concentrated black liquor is combusted in the kraft recovery boiler to produce heat and power and to convert the inorganic substances into regenerable forms. Sodium and sulfur compounds are converted under reducing conditions into a liquid phase called the smelt, consisting of Na2CO3 and Na2S. The smelt flows from the furnace floor to a dissolving tank for further processing where the alkaline cooking solution is recovered. A schematic diagram of the processes and streams in the chemical recovery cycle of a typical kraft pulp mill is shown in Figure 1.1.
Chapter 1- Introduction
H2O
CHIPS
Pulping
WHITE LIQUOR
Washing
PULP FIBRES
H 2O
Paper mill
Weak black liquor
Evaporators
Black liquor
Recovery boiler
Smelt
Flue gases Steam Electricity
Dissolver
Green liquor Lime mud
Flue gases
Causticising
Lime
Lime kiln
Figure 1.1. Schematic diagram of chemical recovery in the kraft pulping process The dual role of the kraft recovery boiler as both a chemical reactor and a heat/power boiler presents unique challenges compared to traditional heat and power boilers. Not only should the heat be recovered and emissions kept low, but also a chemical product of the desired quality should be produced. The fuel, black liquor, adds to the complexity of the processes in the kraft recovery boiler, because it contains large amounts of sodium and sulfur originating from the cooking chemicals. This gives it unusual combustion properties compared to other fuels, which can lead to serious problems with fouling, plugging, and corrosion in the recovery boiler. In many of the processes in the kraft recovery boiler, the role of inorganic alkali compounds is central. The main reaction related to chemical recovery in the boiler, the reduction of sulfur to the preferred sulfide species S2-, involves reactions between char carbon and molten sodium compounds containing sulfurous anions [1]. In addition, organically associated sodium plays an important catalytic role in the conversion of the
char carbon [2-4]. In some of the more problematic aspects of operations in the recovery boiler, like fouling, plugging, and corrosion, the role of molten salts is significant. The behavior of molten salts is also of great interest when developing new technologies or concepts for chemical recovery from black liquor. In the direct causticizing or autocausticizing concepts, chemicals are added to or are present in the chemical recovery cycle in order to decrease the load on the causticizing units of the pulp mill. Many of the important reactions involved occur in the liquid phase in the recovery boiler [5]. The chemical behavior of the various alkali compounds and their mixtures is of utmost importance for processes occurring in the kraft recovery boiler and other similar devices. Several approaches are required to investigate the behavior of the alkali compounds and their mixtures in the kraft recovery boiler, and to predict how they affect the processes. Experimental studies are the basis for understanding the chemical processes in the recovery boiler. Data on the chemical equilibrium of reactions, rates of reactions, and mass transfer of the different phases and species are needed to understand the chemical reactions in the kraft recovery boiler. However, in the study of complex chemical processes, such as the combustion of black liquor and the reactions related to chemical recovery occurring on such a large scale, the need for proper modeling tools arises. Thermodynamic modeling gives the equilibrium composition of phases and species under specified conditions, while chemical kinetics modeling takes into account the temporal variation of the chemical reactions. Additional models for diffusion in particles and for fluid flow are essential, as thermodynamic modeling does not consider how particles come into contact with each other, which is important when chemical reactions involve two or more reactants. To obtain a comprehensive understanding of the chemistry in the kraft recovery boiler requires all the above-mentioned modeling approaches plus other models. Computational fluid dynamics (CFD) can be used to construct comprehensive models of the processes in the kraft recovery boiler, but the validity of such simulations is dependent on the various submodels that are used. Thermodynamic modeling is often used to predict the melting properties of the inorganic condensed phases in the boiler; it is based on Gibbs energy minimization techniques, assuming that the Gibbs energy of all phases is known. For the thermodynamic modeling to be a useful and accurate tool, it is essential to have a
consistent set of thermodynamic data for all phases. The thermodynamic data for solution phases must also be modeled, which requires the choice of appropriate solution models. The Calphad method is a procedure to evaluate the phase equilibrium and thermodynamic data and to optimize the Gibbs energy functions of the phases involved. With an appropriate description of the thermodynamic properties of the alkali salt mixtures, several important phenomena in the kraft recovery boiler can be modeled and understood, such as melting of the recovery boiler smelt and superheater deposits, sulfur reduction reactions, autocaustizing reactions, and volatilization of alkali compounds.
1.1 Objective of the study

The objective of the present study was to gain a better understanding of the reactions and phase relations of alkali salts in the kraft recovery process. The thermodynamic properties of the alkali salt mixtures typically found in the kraft recovery boiler, mainly sodium and sulfur-containing salts, were evaluated and optimized based on experimental data from the literature to obtain a consistent thermodynamic database. The database can be used to model and shed light on phenomena occurring in the kraft recovery boiler, such as smelt bed behavior, deposit formation and corrosion. The main emphasis was on the solid-liquid equilibrium of alkali salt mixtures, but the solid phase equilibrium and the solid-liquid-gas equilibrium were also studied. Additional experiments were conducted for ternary systems to produce new input data for the thermodynamic evaluation. In addition, an experimental study was carried out on the reactions of borates in alkali salt mixtures to understand the effect of chemical components and physical conditions on the borate autocausticizing concept. The results can be used as input for future thermodynamic evaluations of alkali borate mixtures, which play an important role in the combustion of boron-containing black liquors.
Chapter 2-Alkali salts in the recovery boiler 2. Alkali salts in the recovery boiler
Black liquor is a complex material consisting of water, organic residues from pulping, and dissolved or solid inorganic compounds. The specific properties and composition of black liquor are dependent on the raw material and the processes used by the pulp mill. The primary organic compounds are lignin, polysaccharides, carboxylic acids and extractives. The inorganic compounds are alkali salts such as Na2CO3, Na2S, Na2S2O3, Na2SO3, Na2SO4, NaCl, NaOH, NaHS, Na2Sx, and corresponding potassium compounds [6]. These salts may be solid or dissolved, depending on the water content of the black liquor. A large part of the sodium and sulfur that forms inorganic salts in the recovery boiler exists in organic compounds in the black liquor. The speciation of the elements in the black liquor is dependent on the pulp mill processes and can vary considerably within a pulp mill and between different mills. The elemental composition of typical Scandinavian and North American virgin black liquors is given in Table 2.1. The main difference between the elemental composition of black liquor and that of solid fuels such as coal, wood, and straw, is the higher concentration of sodium and sulfur. Black liquor has unique characteristics as a fuel due to its high water content and the high inorganic material content, which give it low heating values compared to other fuels. Table 2.1. Typical elemental composition (in wt-%) of black liquor from softwood and hardwood black liquors from Scandinavia and North America on a dry solid basis [6].
Scandinavian wood Element Carbon, % Hydrogen, % Nitrogen, % Oxygen, % Sodium, % Potassium, % Sulfur, % Chlorine, % Others, % Softwood (pine) Typical 35.0 3.6 0.1 33.9 19.0 2.2 5.5 0.5 0.2 Range 32-37 3.2-3.7 0.06-0.12 33-36 18-22 1.5-2.5 4-7 0.1-0.8 0.1-0.3 Hardwood (birch) Typical 32.5 3.3 0.2 35.5 19.8 2.0 6.0 0.5 0.2 Range 31-35 3.2-3.5 0.14-0.2 33-37 18-22 1.5-2.5 4-7 0.1-0.8 0.1-0.3 North American wood Softwood (pine) Typical 35.0 3.5 0.1 35.4 19.4 1.6 4.2 0.6 0.2 Range 32-37.5 3.4-4.3 0.06-0.12 32-38 17.3-22.4 0.3-3.7 2.9-5.2 0.1-3.3 0.1-2.0 Hardwood Typical 34.0 3.4 0.2 35.0 20.0 2.0 4.3 0.6 0.5 Range 31-36.5 2.9-3.8 0.14-0.2 33-39 18-23 1-4.7 3.2-5.2 0.1-3.3 0.1-2.0
Chapter 2-Alkali salts in the recovery boiler

The main purpose of the combustion of black liquor is to produce heat, which can be recovered and utilized for other processes; it also provides energy for the conversion of inorganic compounds into the smelt, which is recovered and processed into the cooking chemicals for the pulping process. Black liquor, which has been dried to a dry solid content of 70-85%, is sprayed as droplets into the recovery boiler furnace. Combustion occurs in several stages: As black liquor droplets enter the furnace, they are dried and water vapor is released. Next, they are heated and gas components with low molecular weights, such as CO, CO2, CH4, H2 and H2S, are released in the pyrolysis or devolatilization stage [7]. The devolatilization stage is usually associated with a considerable increase in the black liquor droplet volume. The combustible gases are burned when they come into contact with oxygen. Finally, the solid char matrix begins reacting with oxygen. Much of the inorganic matter remains in the char, and during the char carbon conversion, the important sulfur reduction reactions occur. The overall reduction reaction can be described by the following equation:
Na2SO4(l) + 2(1+X) C(s) Na2S(l) + 2(1-X) CO2(g) + 4X CO(g), [0 X 1]. [Eq. 2.1] The reduction of sulfate to sulfide is an endothermic process, and the energy required for the reaction is provided by the heat released when the char carbon burns. Organically associated sodium plays an important catalytic role in the conversion of the char carbon [2-4]. As the char carbon burns away, the remaining molten salt coalesces and forms the smelt. If the smelt comes into contact with oxygen, the sulfide can be re-oxidized according to the following reaction:
Na2S(l) + 2 O2(g) Na2SO4(l)
[Eq. 2.2]
In reality all the different stages of black liquor droplet combustion overlap [8, 9]. Ideally, in the recovery boiler, the drying and the devolatilization steps take place in flight before the droplets reach the char bed at the bottom of the furnace. Char

combustion and sulfur reduction take place on the char bed, and the smelt containing Na2S and Na2CO3, is removed from the recovery boiler before re-oxidation occurs. In addition to the combustion of black liquor and the sulfur reduction, there are other processes involving alkali compounds that are important for the operations of the recovery boiler. The volatilization and condensation of alkali salts play an important role in the formation of so-called fume, which can cause unwanted deposit buildup on heat exchangers. Also, Na2CO3 can react with carbon, producing sodium vapor, CO, and CO2 in the recovery boiler [10]. The overall reaction is given by Equation 2.3:
Na2CO3(s,l) + X C(s) 2 Na(g) + (2X-1) CO(g) + (2-X) CO2(g) [0.5X2].
[Eq. 2.3]
The formation of gaseous Na-compounds is enhanced by the higher furnace temperatures achieved by lowering the water content of the black liquor. The condensation of the alkali vapors is related to fume formation in the boiler, which can cause deposit buildup on heat exchangers. The fume particles generally have a diameter of about 0.1 to 1 m [11]. In modern boilers, which burn black liquor with a high dry solids content, SO2 emissions are very low because SO2 reacts with gaseous Na-compounds to form condensed Na2SO4, which makes up a large part of the fume particles. Moreover, NaCl and KCl are also enriched in the fume because the chlorides have higher volatility than the other alkali compounds in the boiler. The formation of alkali salt deposits on heat exchanger surfaces is also related to the formation of carryover particles. Carryover particles are black liquor droplets or fragments of burning droplets that are mechanically entrained by the furnace gases. The size of carryover particles varies between 20 m and 3 mm [11]. Their composition is similar to that of oxidized smelt, as the particles originate from entrained smelt or black liquor particles. However, mature carryover deposits generally have higher sulfate concentration due to sulfation of carbonates and/or chlorides. The deposits in the kraft recovery boiler are mixtures of fume particles and carryover particles in a ratio which varies in different parts of the boiler. Corrosion in the recovery boiler is often related to the presence of molten alkali salts. The existence of low-melting sodium polysulfides (Na2Sn, n>1) in the char bed has 7

been suggested by Backman et al. [12] as a source of furnace floor corrosion. The alkali polysulfides melt at considerably lower temperatures than a mixture of Na2CO3, Na2SO4, and Na2S. Generally, the floor temperatures are kept below the melting temperatures of the smelt. However, the existence of a liquid phase in contact with the furnace floor may cause corrosion of the floor material at low temperatures. Corrosion of superheaters is often attributed to molten salt corrosion [13]; a liquid phase in the deposits is the corrosive agent. High concentrations of chlorides in the deposits usually give low firstmelting temperatures and are often related to increased corrosion of the superheaters. However, the mechanisms of chlorine-induced corrosion are not fully understood. Formation of low-melting acidic sulfates, such as alkali disulfates (Na2S2O7, K2S2O7) and alkali hydrogen sulfates (NaHSO4, KHSO4), are also related to corrosion in recovery boilers burning black liquors with high sulfur contents [14]. Alkali borate compounds also play an important role in the autocaustizing concept in recovery boilers firing borate-containing liquors. The behavior of alkali borates is discussed in detail in Section 4.
Chapter 3-Thermodynamic modeling 3. Thermodynamic modeling of alkali salt mixtures involved in black liquor combustion
3.1 Overview of the properties of ionic compounds and solutions

The solid and liquid alkali compounds in a kraft recovery boiler are ionic compounds. The solid sodium and potassium compounds, such as Na2SO4, Na2CO3 and KCl, are often called salts. The term salt has traditionally been used for table salt or rock salt (NaCl) and for the ionic solid product that is formed when a metal hydroxide or oxide (base) reacts with an acid. The term molten salt is commonly used both in industry and in the scientific community to describe high-temperature ionic liquid phases. The term ionic liquid is mainly used for low or room temperature liquids of an ionic nature. Ionic compounds consist of electrically charged components, anions and cations, which are attracted to or repelled by each other due to Coulomb forces. The result is that ionic crystals have strong ordering, in which anions are surrounded by cations and cations are surrounded by anions in the crystal lattice. The anions reside on an anionic sublattice, with cations as the nearest neighboring ions, and vice versa for the cations. Ionic compounds usually have low volatility and high melting temperatures (except for room temperature ionic liquids), and in the liquid state, they are electrically conductive due to the mobility of the ions. In the liquid state, the ions are also arranged with anions surrounded by cations, and vice versa. Due to their mobility in the liquid state, the ions are not restricted to fixed lattice sites, but for modeling purposes quasi-sublattices for the anions and cations are used to describe the thermodynamic properties of ionic liquid phases [15-18]. Ionic melts have great importance in many industrial fields. In the manufacture of aluminum, molten cryolite (Na3AlF6) is the base solvent for Al2O3 in Hall-Hroult electrolysis cells [19]. Molten alkali and alkaline earth chloride mixtures are used as electrolytes in the production of metallic sodium and magnesium, where the corresponding chloride is electrolyzed to the metallic form, and the other chloride salts act as fluxes to lower the melting temperature of the mixture [19]. In the molten
Chapter 3-Thermodynamic modeling

carbonate fuel cell (MCFC) and the sodium-sulfur battery [20], which have been developed for medium-scale electricity production, ionic melts play an important role in the electrochemical reactions. The molten salt reactor (MSR) [21] is considered to be a promising type of nuclear reactor belonging to the class known as generation IV reactors. In this type of reactor, the fuel is uranium or plutonium fluorides dissolved in a molten mixture of NaF and ZrF4. Silicate melts, which consist of polymeric ionic species, are used for example in glass manufacturing. Ionic melts play an important role in chemical reaction engineering. In the production of sulfuric acid, a molten mixture of alkali disulfates and V2O5 is the catalyst for the oxidation reaction of SO2 to SO3 in the contact process [19]. Low temperature or room temperature ionic liquids, which are molten organic salts, are becoming increasingly important as solvents and catalysts in chemical reaction engineering because of their thermal stability, low volatility, and ability to dissolve different types of chemical substances. The ionic species in ionic liquids are usually much more complicated than those in many inorganic salts, and the ionic liquids can be tailor-made for the specific purposes. The production of smelt in kraft pulping is one of the largest molten salt producing chemical processes today. About 200 million tons of black liquor dry solids are produced annually worldwide [22], and roughly one third of the mass is transformed into smelt, which is used for the production of pulping chemicals
3.2 Thermodynamic equilibrium modeling

In order to predict the chemical behavior of multicomponent multiphase systems, computational methods are needed to calculate the chemical equilibrium, the reaction kinetics, and the transport properties of the species of interest. This becomes very complicated for systems involving solid phases, a liquid phase, and a gas phase, especially if the chemical composition of the phases varies. The mathematical models need experimental data as input for the model parameters. Unfortunately for many
10

complex systems, these data do not exist or experimental results are too complicated to use for extracting model parameters. Therefore, a good description of the chemical behavior in simplified systems is essential for making predictions in more complicated systems. Thermodynamic modeling is a commonly used tool for predicting the chemical behavior of complex systems. It is often based on minimization of the Gibbs energy of the system, which can be calculated using modern software if thermodynamic data exist for all the phases considered. Thermodynamic data for multicomponent solution phases are based on the thermodynamic data of the end-member components and on the interaction parameters of the solution model describing the Gibbs energy of the solution phase. Thermodynamic modeling is also important in kinetic modeling [23] and in modeling diffusion in alloys [24]. The computational methods involved in calculating multiphase multicomponent thermodynamic chemical equilibrium revolve around Gibbs energy minimization [23]. The classical method of calculating the phase equilibrium from equilibrium constants is not suitable for large multicomponent multiphase systems. The true chemical equilibrium can be calculated by considering the Gibbs energy of all phases and minimizing the total Gibbs energy of the system (G). Here, G can be calculated either from the knowledge of the chemical potential ( Gi , i) of component i, by
G = ni Gi ,
i
[Eq. 3.1]
where ni is the amount of component i, or alternatively by

G = N Gm ,
[Eq. 3.2]
where N is the amount of the phase and Gm is the Gibbs energy of the phase.
For a given set of constraints, such as fixed P, T, and overall composition, the Gibbs energy minimization algorithms find the amounts of the various phases and the composition of the solution phases which give a global minimum in the total Gibbs energy of the system. One of the best-known Gibbs energy minimization programs is
11

SOLGASMIX by Eriksson [25]. This program has evolved over the years and is currently an integral part of the thermochemical software package FactSage [26]. In the present study, all thermodynamic calculations were performed using FactSage. Several other programs have also been developed for thermochemical calculations. An entire issue of the Calphad Journal is dedicated to reviews of many existing programs (Volume 26, issue 2, 2002).
3.3 Optimization of phase diagrams and thermodynamic data

Phase diagrams and phase equilibria can be calculated if the Gibbs energy functions of all phases involved are known. If the Gibbs energy functions for a phase are not known but experimental data for phase equilibrium or thermodynamic properties exist, it is possible to obtain a thermodynamic description of the phase through an optimization procedure, often called the Calphad method. The principle underlying the Calphad method is to obtain a set of consistent Gibbs energy functions for all phases in the system of interest by using experimental thermochemical and phase equilibrium data as input [27]. In many cases, the main emphasis is on optimizing the Gibbs energy functions of the solution phases, which in reality means optimizing the interaction parameters of various solution models. The Gibbs energy functions are obtained by weighted nonlinear optimization of the thermochemical and phase equilibrium data. Several of the commercially available thermodynamic software packages include programs for these optimization. The Optisage module in FactSage [26] was used in the present study. The optimization algorithm in the program is a nonlinear Bayesian least squares technique [28-30]. The general procedures for optimizing phase diagrams and thermodynamic data with the Calphad method are described by Hari Kumar and Wollants [27] and Schimd-Fetzer et al. [31].
12
Chapter 3-Thermodynamic modeling 3.4 Thermodynamic models of ionic solutions

The thermodynamic properties of solution phases as function of composition must be known to calculate phase equilibrium involving the solutions. For this purpose, different thermodynamic models have been developed to describe the thermodynamic properties of solutions. Solution phases are the gas phase, liquid phases and solid solutions. The gas phase is a solution phase, which shows complete miscibility of all gas species. The nonideal behavior of the gas phase can be modeled by several different approaches. The van der Waals equation was one of the first steps to introduce nonideality to the behavior of real gases, taking into account the interaction between gas molecules. At the high temperatures and the atmospheric pressure in a kraft recovery boiler, the non-ideality of gases is usually not very pronounced; therefore, models for the nonideality of gases is not treated further in this work. The solution models that are treated in more detail have been developed for solid solutions or liquid solutions. Several of these models are often used for both solids and liquids. For all solution phases, the Gibbs energy is given by the general formula
ideal excess , G = G + Gmix + Gmix
[Eq. 3.3]
where G is the contribution of the pure components of the phase to the Gibbs energy,
ideal excess is the ideal mixing contribution, and Gmix is the excess Gibbs energy of mixing, Gmix
which is the contribution involving the non-ideal interactions between the components.
3.4.1 Ideal solutions
The simplest solution model is an ideal substitutional solution or the Raoultian solution. This approach is valid for an ideal gas phase and may be valid for simple metallic liquid or solid solutions, where the components show very similar behavior. The ideal substitutional solution is characterized by random distribution of components on one lattice with an interchange energy equal to zero. For the gas phase and liquids, no actual lattice exists as the crystallographic structure is lost, but for modeling purposes a quasi13

lattice or defined spatial positions are used to model the mixing of particles. For an ideal
excess substitutional solution, the excess Gibbs energy of mixing ( Gmix ) is zero, and as it is
assumed that there is no change in bonding energy or volume upon mixing, the enthalpy of mixing is also zero:
ideal =0. H mix
[Eq. 3.4]
The Gibbs energy of mixing is therefore given by the following expression:

ideal ideal . Gmix = TS mix
[Eq. 3.5]
ideal The term S mix is related to the Boltzmann equation for configurational entropy, which
deals with the entropy associated with random distribution of particles over a given
ideal number of positions, and S mix is given by the following expression:
ideal S mix = R xi ln xi . i
[Eq. 3.6]
The molar Gibbs energy of an ideal solution is

Gm = xi Gio + RT xi ln xi ,
i i
[Eq. 3.7]
where Gio is the Gibbs energy of the phase containing the pure component i. Ideal solutions are uncommon for condensed phases as there usually is some interaction between the components of the solution.
3.4.2 Nonideal solutions
The regular solution model is the simplest thermodynamic model for nonideal solutions. The regular solution model considers that the magnitude and sign of the interactions between components in a phase are independent of composition. If the total energy of the solution (E0) originates from only nearest-neighbor bond energies in a system A-B then
E0=AAEAA+BBEBB+ABEAB,
[Eq. 3.8]
14

where AA, BB, AB are the number of bonds and EAA, EBB, EAB are energies associated with the formation of different bond types AA, BB and AB. If there are N atoms in the solution and the coordination number for nearest-neighbors is Z, the number of different bond types formed in a random solution will be
2 AA = NZx A ,
1 2
[Eq. 3.9.1] [Eq. 3.9.2] [Eq. 3.9.3]

B
2 BB = NZxB ,
1 2
AB = NZx A xB ,
where xA and xB are the mole fractions of A and B. By substituting Equations 3.9.1-3.9.3 into Equation 3.8, the total energy of the solution will be given by the expression
E0 =
NZ ( x A E AA + xB EBB + x A xB (2 E AB E AA EBB )) . 2
[Eq. 3.10]
By subtracting the energy of pure A and pure B from Equation 3.10, the energy change for mixing A and B to an A-B solution will be
E =
NZ ( x A xB (2 E AB E AA EBB )) . 2
[Eq. 3.11]
One can approximate that E Hmix, where Hmix is the enthalpy of mixing. If the bond energies are temperature-dependent, there will also be a term for excess entropy of mixing, which can be derived in a similar fashion as for Hmix. The excess Gibbs energy of mixing for the regular solution model is given by
excess excess Gmix = H mix TS mix = x A xB ,
[Eq. 3.12]
where is a composition-independent, temperature-dependent interaction parameter. The general expression for the Gibbs energy of a regular solution is as follows:
Gm = xi Gio + RT xi ln xi + xi x j ij .
i i i j >i
[Eq. 3.13]
However, it has been realized that the assumption of composition-independent parameters for the excess Gibbs energy is too simple for many systems. The approach where the interaction terms change linearly with composition is called a subregular
15

solution model. Even more complex compositional dependencies can be adopted. The Redlich-Kister form, (xA-xB)n, where n is a positive integer, is a common form of
B
expressing composition-dependent terms of the excess Gibbs energy. The Gibbs energy of the solution with the excess Gibbs energy expressed in Redlich-Kister form is
n Gm = xi Gio + RT xi ln xi + xi x j ij ( xi x j ) n , [Eq. 3.14] i i i j >i n
n where the term ij is a binary interaction parameter dependent on the value of n.
Equation 3.14 will reduce to Equation 3.13 if n=0. According to Saunders and Miodownik [23], the value of n does not usually go above 2. If higher power expansions are needed to describe Gexcess, an incorrect model has probably been chosen to model the solution. Other equivalent polynomial expansions, such as a simple power series or Legendre expansions are also used [32].
3.4.3 Sublattice models
Simple nonpolar molecular solutions and ionic solutions, such as molten salts, often exhibit approximately regular solution behavior according to Pelton [33]. Sangster and Pelton [34] showed that the liquid phase and solid solutions in many of the binary common-anion or common-cation systems of alkali halides can be modeled with regular or subregular solution models. However, substitutional solution models are not suitable for more complex ionic solutions with several cations and anions, or where there is a strong ordering of the components in the liquid phase, which is the case for some alkali halide-alkaline earth halide systems. In a review of thermodynamic models for molten salts and slags, Pelton [35] showed that an associate model will not predict the phase equilibrium satisfactorily for ionic solutions, such as K+, Li+//Cl-, F-, where LiF, LiCl, KF and KCl are the solution components. Instead, models that take into account physical properties of the ionic
16

solutions are needed. Temkin [16] was one of the first to propose a thermodynamic model of ionic solutions, in which two sublattices are considered. The cations reside on one sublattice and the anions reside on the other sublattice. The configurational entropy is governed by the site occupation of the various cations and anions on their respective sublattices. For a simple reciprocal ionic solution A, B/X, Y, where the cations A and B, and the anions X and Y have the same absolute value of their ionic charge, the Gibbs energy of the solution is given by the following expression:
cation anion o cation anion o cation anion o cation anion o cation cation Gm = xA x X GAX + x A xY GAY + xB xX GBX + xB xY GBY + RT ( x A ln( x A ) cation cation anion anion anion anion + xB ln( xB )) + RT ( x X ln( xX ) + xY ln( xY )) + G E .
[Eq. 3.15] The term xisublattice is the site fraction of a sublattice component i on the sublattice, and
o G AX is the Gibbs energy of the pure component AX. If the valence of the cations and
anions varies, the modeling will become more complex. Pelton [36] developed a sublattice model for molten salts, in which equivalent cationic and anionic fractions are used instead of site fractions. The equivalent fractions are defined as
Yi = qi ni / qi ni .
i
[Eq. 3.16]
The term qi is the absolute charge of the ion i, and ni is the number of moles of i on the sublattice. The Gibbs energy of the solution is given by the expression
o Gm = YAYX G AX +RT (( q X x X ) 1 ( x X ln x X ) + ( q A x A ) 1 ( x A ln x A )) + G E . A X
[Eq. 3.17] A thermodynamic database for the Li+, Na+, K+//F-, Cl-, OH-, CO32-, SO42- system has been developed using the sublattice model for molten salts [36], which gives good estimates of the thermodynamic properties of multicomponent liquids. Hillert et al. [18] also developed a sublattice model for ionic solutions, which is known as the ionic two-sublattice model for liquids. The model can accommodate hypothetical charged vacancies and neutral species on the anionic sublattice, meaning
17

that the solution composition can vary between a metallic state and a fully ionized state. More in-depth descriptions of the sublattice models are given by Pelton [36] and Hillert et al. [18].
3.4.4 Compound Energy Formalism
The Compound Energy Formalism is a mathematical formalism, which is commonly used for describing the thermodynamic properties of solutions that are modeled with sublattice solution models. In the present work, the thermodynamic properties of all multicomponent solid solutions are described using the Compound Energy Formalism [37, 38]. Sodium and potassium salts, such as sulfates, disulfates, carbonates, and chlorides, tend to form complex solid solutions. In general, these solid salt solutions can be considered to consist of sublattices, which contain the ionic components. In the simplest case with two sublattices, one sublattice contains the cations, such as K+ and Na+, and the other sublattice contains the anions, such as SO42- and CO32-. More complicated sublattice configurations may be considered. The solid solution might have several cationic crystal sites, where one cation is preferred on one site, and another cation is preferred on another site. A classical example is the spinel phase, AB2O4, where A2+ resides on sites with tetrahedral coordination, and B3+ resides on sites with octahedral coordination. The phase can be considered to consist of three sublattices, as O2- resides on a third, anionic sublattice. For the reciprocal solution phase (A,B)m(C,D)n, where the species A and B reside on the sublattice S, and the species C and D reside on a second sublattice T, the molar Gibbs energy of the solution is given by the following expression:
S T o S T S T o S T o o Gm = y A yC GA:C + y A yDGA : D + y B yC GB:C + y B y D GB: D S S S S T T T T + (mRT ( y A ln y A + yB ln yB ) + nRT ( yC ln yC + yD ln yD )) + G E .
[Eq. 3.18]
18

S The first four terms give the reference Gibbs energy of the solution, where y A is the site
o fraction of species A on sublattice S, G A :C is the standard molar Gibbs energy of the end-
member component AmCn, and correspondingly for the other sublattice species and endmember components. The two following terms give the ideal entropy of mixing (Temkin type [16]), assuming a random distribution of the sublattice species on their respective sublattices, and the final term is the molar excess Gibbs energy. The excess Gibbs energy is given by the following expression:
S S T S S T S T T S T T S S T T G E = yA y B yC LA,B:C + y A yB yD LA,B:D + y A yC yD LA:C ,D + y B yC yD LB:C ,D + y A yB yC yD LA,B:C ,D
[Eq. 3.19] The four first terms are interaction parameters of the four binary subsystems, and the last term is a reciprocal interaction parameter. The L factors can be temperature- and composition-dependent, commonly given as Redlich-Kister terms as function of the site fraction.
3.4.5 Modified Quasichemical Model in the Quadruplet Approximation
The regular solution model and modifications of it, together with sublattice models mentioned above, assume that the mixing of particles is random, even when the excess Gibbs energy is not zero. However, several systems show considerable short-range ordering in the liquid phase, especially oxide systems where polymeric units are present. Examples are silicate, borate and phosphate liquids. Similar strong short-range ordering can be found in many binary liquids consisting of alkali halides together with divalent or trivalent metal halides. The Quasichemical Model was developed by Guggenheim [39] and Fowler and Guggenheim [40] to take into account non-random short-range ordering in solutions. Pelton and Blander [41] and Blander and Pelton [42] modified the model, with further developments made by Pelton and Chartrand [43], Chartrand and Pelton [44], and Pelton et al. [17, 45], by making the model more flexible and by merging the 19

quasichemical model with sublattice models. The article by Pelton et al. [17] on the Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation is the latest development of the Modified Quasichemical Model, permitting the treatment of both first-nearest-neighbor and second-nearest-neighbor short-range ordering simultaneously in molten salt solutions. For the liquid solution, the thermodynamic model must take into account cations and anions being distributed on a cationic and an anionic quasi-sublattice. If there are two or more cations and two or more anions in the solution, the phase will be a multicomponent reciprocal solution. Large deviations from ideal mixing can occur in reciprocal molten salt solutions due to the strong first-nearest-neighbor (cation-anion) interactions. Simultaneously, strong second-nearest-neighbor (cation-cation, or anionanion) interactions can occur, making modeling of such systems difficult. The Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation [17] was used in the present work to model the Gibbs energy of the liquid phase. This model was developed particularly for molten salt solutions that exhibit strong short-range ordering (SRO) between ions of opposite charges (first-nearestneighbours, FNN) and between ions of the same charge (second-nearest-neighbors, SNN). The Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation simultaneously evaluates the impact of all FNN exchange pair reactions (similar to Eq. 3.20) and all reactions involving SNN pairs (similar to Eq. 3.21.1 and 3.21.2) on the configurational entropy:
[K CO3 ]pair + [Na Cl ]pair = [K Cl ]pair + [Na CO3 ]pair
g K , Na / CO3 ,Cl . [Eq. 3.20] g Na , K / SO4 , [Eq. 3.21.1] g Na / CO3 , SO4 .
[Na SO4 Na ]pair + [K SO4 K ]pair = 2[Na SO4 K ]pair
[CO3 Na CO3 ]pair + [SO4 Na SO4 ]pair = 2[CO3 Na SO4 ]pair
[Eq. 3.21.2] If the standard Gibbs energies of Eq. 3.20 and Eq. 3.21 are negative, the equilibrium will be shifted to the right and FNN and SNN pair concentrations will be affected accordingly (resulting in FNN SRO and SNN SRO). If the values of the standard Gibbs energies of Eq. 3.20 and Eq. 3.21 are close to zero, the model will be reduced to a random mixing
20

model. In the model, each quadruplet consists of 2 cations and 2 anions forming a configurational unit that includes 4 FNN pairs and 4 SNN pairs. Each quadruplet has Gibbs energy, and the parameters of the model are the energies of the quadrupletformation reactions. The quadruplets mix randomly and are constrained by an elemental mass balance. Overlapping of sites and pairs is considered in the configurational entropy. The Gibbs energy of the quadruplets is defined as follows: The Gibbs energy of a unary quadruplet consisting of two cations A and two anions X is
2q A go A2 / X 2 = A Z A2 / X 2 o 2q X g A X = X 1/ qA 1/ qX Z A 2 / X2 o gA X , 1/ qA 1/ qX [Eq. 3.22]
A is the secondwhere qA and qX are the absolute charges for the ions A and X, Z A 2 / X2
nearest neighbor coordination number of A when all A exist in A2X2 quadruplets, and
go is the standard Gibbs energy of the related pure component per charge A1 / q A X1 / q X
equivalent. The term g o A2 / X 2 is the standard Gibbs energy of Aq X X q A per mole of A2X2 quadruplets. For binary common-anion quadruplets, such as ABX2, and similarly for binary common-cation quadruplets, such as A2XY, the following reaction between unary quadruplets can be considered: [A2X2]quad + [B2X2]quad = 2[ABX2]quad. [Eq. 3.23] The Gibbs energy change of the reaction is g AB / X 2 . The term g AB / X 2 is an empirical parameter of the model and can be expressed as
o g AB / X 2 = g o AB / X 2 + ( g AB / X 2 g AB / X 2 ) ,
[Eq. 3.24]
where g o AB / X 2 is a function of temperature only, independent of composition, and (g AB / X 2 g o AB / X 2 ) is expanded as an empirical polynomial in the quadruplet mole fraction, xij / kl . The Gibbs energy of the binary quadruplet ABX2 is given by the following expression:
A ZA 2 / X2 2g o = AB / X 2 A Z AB / X2
o ZB g A / X + B2 / X 2 B 2 2 Z AB / X2
o g B / X + g o AB / X 2 . 2 2
[Eq. 3.25]
If g AB / X 2 = 0, the binary AX-BX liquid solution will be reduced to an ideal solution. For the Gibbs energy of the reciprocal quadruplet ABXY, g o AB / XY , the formation of the
21

reciprocal quadruplet from the unary and binary quadruplets is considered. For the quadruplet formation reaction (ABX2 + ABY2+A2XY+B2XY) = 2(ABXY), [Eq. 3.26]
o the Gibbs energy change is g AB / XY . The term g AB / XY = g o AB / XY + ( g AB / XY g AB / XY )
is an empirical parameter of the model, where g o AB / XY is a function of temperature only, and ( g AB / XY g o AB / XY ) is expanded as an empirical polynomial in the quadruplet mole fraction, xij / kl . The Gibbs energy of the reciprocal quadruplets is given by the following expression [17]:
g + +
o AB / XY
qX q = + YY ZX AB / XY Z AB / XY go A2 / Y2 + +
A B qX Z A qX Z B o o 2 / X2 2 / X2 A g A2 / X 2 + gB X B X 2 / X2 2Z AB XY Z AB XY Z Z 2 AB / XY AB / XY / / X Y 1 Z AB Z AB / Y2 / X2 o o g gB + + g o AB / X 2 AB / Y2 X Y 2 / Y2 Z AB / XY 4 Z AB / XY
A qY Z A 2 / Y2 A Y 2 Z AB / XY Z AB / XY A ZA 2 / XY A Z AB / XY
B qY Z B 2 / Y2 B Y 2Z AB / XY Z AB / XY
o A2 / XY
B ZB 2 / XY B Z AB / XY
o + g o g B AB / XY 2 / XY [Eq. 3.27]
The parameters g AB / X 2 , g AB / Y2 , g A2 / XY and g B2 / XY are obtained from optimization of thermodynamic and phase diagram data that involve the liquid phase in the binary common-ion subsystems. The parameter g AB / XY is obtained from optimization of thermodynamic and phase diagram data in the ternary reciprocal system. Empirical ternary parameters may also be added to common-ion ternary systems of the type AX-BX-CX. The ternary parameter gives the effect of a third component, CX, on the quadruplet-formation energy of the binary AB/X2 quadruplet, g AB / X 2 . As described by Pelton and Chartrand [43] and Pelton et al. [17], this is done by introducing
ijk the empirical ternary parameter g ijk AB ( C ) / X 2 . The parameter g AB ( C ) / X 2 is obtained from
optimization of thermodynamic and phase diagram data in the common-ion ternary system. The functions of the binary interaction parameters of the type g AB / X 2 and
g A2 / XY , taking into account the effect of the ternary interaction parameters are given by
Pelton et al. [17] (Equations 46-48 in reference [17]).
22

The Modified Quasichemical Model takes into account non-random mixing of particles in the solution. Therefore, an expression for the configurational entropy of mixing, Sconfig, similar to Equation 3.6 cannot be used, as Equation 3.6 is an expression for random distribution of particles. An exact expression for the distribution of all quadruplets over quadruplet positions is not known, but Pelton et al. [17] proposed an approximate expression for the configurational entropy, which is given by Equation 3.28 for a solution in the A,B/X,Y system:
( S config / R) = ( n A ln x A + nB ln xB + n X ln x X + nY ln xY ) + ( n A / X ln + n A / Y ln n A2 / Y2 ln n AB / Y2 ln
xA/ X x + nB / X ln B / X YAYX YBYX
xA / X2 xB / X 2 xA/Y x + nB / Y ln B / Y ) + ( n A2 / X 2 ln 4 2 2 + n A2 / X 2 ln 4 2 2 + 2 YAYY YBYY x A / X /(YA YX ) xB / X /(YB YX2 ) x A2 / Y2

4 A/Y
/(Y Y ) x AB / Y2
2 2 A Y
+ nB2 / Y2 ln
xB2 / Y2 x
4 B /Y
/(Y Y )
2 2 B Y
+ n AB / X 2 ln x A2 / XY
2x
2 A/ X
AB / X 2 2 2 B/ X A B X
/(Y Y Y )
+ xB2 / XY
2 2 2 2xA / Y x B / Y /(YAYBYY )
+ n A2 / XY ln
2 2 2 2xA / X x A / Y /(YA YX YY )
+ nB2 / XY ln
2 2 2 2 xB / X x B / Y /(YB YX YY )
+ n AB / XY ln
x AB / XY ) 4 x A / X xB / X x A / X x B / Y /(YAYBYX YY ) [Eq. 3.28]
The term ni gives the number of moles of a species i, ni/k is the number of moles of firstnearest-neighbor pairs and nij/kl denotes the number of moles of unary, binary and reciprocal quadruplets. The term xi denotes the site fractions, xi/k is the FNN pair fraction and xij/kl is the quadruplet fraction. The Modified Quasichemical Model in the Quadruplet Approximation requires the assignment of coordination numbers of a quadruplet species in the unary, binary and reciprocal quadruplets. The first-nearest-neighbor coordination number is denoted by zi, and gives the number of first-nearest-neighbor pairs emanating from a species i. The second-nearest-neighbor coordination number is denoted by Zi, and gives the number of second-nearest-neighbors pairs emanating from species i. Pelton et al. [17] made the assumption that the ratio between SNN and FNN coordination numbers for a species i is constant and is given by the expression: Zi/zi=/2. [Eq. 3.29]
23
Chartrand and Pelton [46] set the parameter to 2.4 for liquid alkali-alkaline earth halide systems, and in the present study it was set to the same value. For the quadruplet
A approximation, Z AB gives the SNN coordination number of a species A when / XY
(hypothetically) all of A exist in ABXY quadruplets. In the present work the SNN coordination numbers for the quadruplets are as follows:
A A A A ZA = Z AB / X 2 = Z A2 / XY = Z AB / XY = 3 2 / X2 X X X X ZA = Z AB / X 2 = Z A2 / XY = Z AB / XY = 6 2 / X2 A A A A Z Z Z Z ZA = Z AB / Z 2 = Z A2 / ZW = Z AB / ZW = Z A2 / Z 2 = Z AB / Z 2 = Z A2 / ZW = Z AB / ZW = 6 2 / Z2 A A Cl Cl ZA = Z AB / XZ = Z A2 / XCl = Z AB / XCl = 4 2 / XZ X X ZA = Z AB / XCl = 8 2 / XCl Va X X Z Va A2 / XVa = Z AB / XVa = Z A2 / XVa = Z AB / XVa = 6
A, B = Na + , K +
2 2 X , Y = SO4 , CO32 , S 2O72 , S n (n = 1 8)
Z , W = Cl , Va The coordination numbers for quadruplets containing both the charged vacancy (Va-) and a divalent anion are given erroneously in Publication III. The correct coordination numbers are given in the list above. The binary composition variables A2 / XY , A2 / YX , AB2 / X 2 and BA / X 2 are defined as previously [17, 43] as follows:
A / XY = x A / X /( x A / X + x A / XY + x A / Y ) ,
2 2 2 2 2 2 2 2
[Eq. 3.30.1] [Eq. 3.30.2] [Eq. 3.30.3] [Eq. 3.30.4]
A / YX = x A / Y /( x A / X + x A / XY + x A / Y ) ,
2 2 2 2 2 2 2 2
AB / X = x A / X /( x A / X + x AB / X + x B
2 2 2 2 2 2
/ X2
),
BA / X = x B
2
/ X2
/( x A2 / X 2 + x AB / X 2 + x B2 / X 2 ) .
xij / kl denotes the unary, binary and reciprocal quadruplet fractions as defined by Pelton et
al [17]. The Gibbs energy of the solution is given by the model as G = nij / kl g ij / kl TS config , [Eq. 3.31]
24

where nij/kl denotes the number of moles of the unary, binary and reciprocal quadruplets, gij/kl denotes the Gibbs energy of the quadruplets, and Sconfig is the configurational entropy of mixing. Sconfig is calculated from a distribution of all the quadruplets over quadruplet positions by Equation 3.28.
3.4.6 Extrapolation of excess Gibbs energy in multicomponent solutions
Several methods have been proposed for extrapolating the thermodynamic properties of a ternary solution from optimized data of its three binary subsystems. The equations of the extrapolations are based on various geometrical weightings of the mole fractions [47]. The main extrapolation methods are either symmetric or asymmetric. Symmetric methods treat all three binary systems in the same manner, while asymmetric methods treat one of the binaries differently from the two others. Asymmetric extrapolation methods are recommended for ternary systems if two of the components are chemically similar, while the third is chemically different [48]. Examples of such systems are CaO-MgO-SiO2 and NaCl-KCl-AlCl3 where SiO2 and AlCl3 are chemically much different than the other components. The main symmetric extrapolation methods are the Kohler approximation [49] and the Muggianu approximation [50]. The main asymmetric methods are the Kohler/Toop approximation [51] and the Muggianu/Toop approximation [47]. For a ternary A-B-C system, where all binary systems are modeled as subregular solutions with the subregular terms given in Redlich-Kister formalism, the different extrapolation equations are given by Equations 3.32-3.35 (Component A is the asymmetric component in the asymmetric approximations): Kohler approximation: x x xB xC x xB 1 )) + x A xC ( L0AC + L1AC ( A C )) + xB xC ( L0 )) G E = x A xB ( L0AB + L1AB ( A BC + LBC ( x A + xB x A + xC xB + xC [Eq. 3.32]
25

Muggianu approximation: 1 G E = x A xB ( L0AB + L1AB ( x A xB ) + x A xC ( L0AC + L1AC ( x A xC )) + xB xC ( L0 BC + LBC ( x B xC )) [Eq. 3.33] Kohler/Toop approximation: G E = x A x B ( L0AB + L1AB ( x A x B xC ) + x A xC ( L0AC + L1AC ( x A xC x B ))
1 + x B xC ( L0 BC + LBC (
x B xC )) x B + xC
[Eq. 3.34] Muggianu/Toop approximation: G E = x A xB ( L0AB + L1AB ( x A xB xC ) + x A xC ( L0AC + L1AC ( x A xC xB ))

1 + xB xC ( L0 BC + LBC ( x B xC ))
[Eq. 3.35] If all binary systems are regular solutions, Equations 3.32-3.35 will become identical expressions [46, 48]. For additional equations of various approximation models for multicomponent systems, see Hillert [47], Chartrand and Pelton [46] and Pelton [48]. Figure 3.1 shows the geometrical considerations for the symmetric and asymmetric models.
26
Figure 3.1. Geometrical constructions of the Kohler, Kohler/Toop, Muggianu and Muggianu/Toop extrapolation models
3.5 Thermodynamic evaluation and optimization of the Na+, K+/CO32-, SO42-, S2-, S2O72-, Sx2-, Cl-, Va- system
The thermodynamic properties of the phases in the multicomponent Na+, K+/CO32-, SO42-, S2-, S2O72-, Sx2-, Cl-, Va- system were evaluated and optimized in this work. The Modified Quasichemical Model in the Two-Sublattice Quadruplet Approximation [17], was used to model the Gibbs energy function of the liquid phase. The Compound Energy Formalism
27

was used for the complex solid solutions, such as the reciprocal (Na,K)2(CO3,SO4,S) hexagonal phase, while simpler solid solutions, such as solid (Na,K)Cl and solid (Na,K), have previously been modeled with simple substitutional models. The simpler solid solution models can also be presented in the Compound Energy Formalism. The phase equilibrium has not been studied experimentally for all possible binary, ternary or higher-order subsystems. The evaluation has been separated into four parts, which represent multicomponent subsystems containing sulfurous ions, whose every binary subsystem has been studied experimentally previously and has been evaluated and optimized in the present study. The multicomponent subsystems are Na-K-S, Na2SO4K2SO4-Na2S2O7-K2S2O7, Na2CO3-Na2SO4-Na2S-K2CO3-K2SO4-K2S and NaCl-Na2CO3Na2SO4-KCl-K2CO3-K2SO4. All thermodynamic data from unary components to multicomponent systems are internally consistent. The thermodynamic data for the stoichiometric solid phases, liquid phase components and gaseous compounds studied in all the above-mentioned subsystems are given in Appendix A. The solution parameters of the solid solutions are given in Appendix B, and the solution parameters of the liquid phase are given in Appendix C. The phases that have been considered in this study are the gas phase, several stoichiometric solid compounds, several solid solutions, an ionic liquid phase and liquid elemental sulfur. The solid solutions are the hexagonal solid solution of (Na,K)2(CO3,SO4,S), five low-temperature solid solutions of (Na,K)2(CO3,SO4), the glaserite phase (non-stoichiometric K3Na(SO4)2), the cubic (Na,K)Cl solid solution, the cubic (Na,K)2S solid solution, the (Na,K)2S2 solid solution, two (Na,K)2S2O7 solid solutions and the metallic (Na,K) solid solution. The thermodynamic data of the pure compounds were either evaluated and optimized in this study or were taken from thermodynamic data compilations [52-60]. The evaluation and optimization of the Na-K-S system is treated separately from the other simple ionic systems due to the more complex behavior of the Na-K-S system.
28

3.5.1 The Na-K-S system
The chemical behavior of the solid and liquid phases in the Na-K-S system shows a great variation over compositional range. The elements Na and K are low melting, reactive metals, while elemental S shows covalent behavior, forming various polymerized units in the gas, liquid and solid phases. The alkali sulfides and polysulfides are ionic compounds. Na2S and K2S are high-melting compounds compared to the other compounds in the alkali-sulfur systems. Na2S and K2S consist of the ions Na+ or K+ and S2-, while the polysulfides are more complex. Liquid alkali polysulfides form an ionic melt that is a mixture of unbranched Sn2- chains of varying length with the charges at both ends of the chain [61]. The liquid phase shows a great tendency for supercooling and glass formation due to the existence of the long polysulfide chains. The behavior of metal alloys containing small amounts of sulfur is to a large extent unknown, and the behavior of molten sulfur is quite complex [62]. The phase equilibria between gas, solid and liquid, and the thermodynamic properties of the liquid phase in the Na-S system have been widely investigated [60, 6374]. The K-S system is not as widely studied [64, 75-80], and no gas phase/condensed phase equilibrium has been reported. The phase relations and the thermodynamic properties of the Na-K system have been reported in references [81-86]. Reviews of the physicochemical properties of the liquid and solids in the K-S and Na-S systems have been made by Sangster and Pelton [87, 88], Morachevskii [73, 89] and Borgstedt and Guminski [90]. The Na-K system has previously been evaluated by Bale [91]. The thermodynamic properties for all known phases in the Na-K-S system were evaluated and optimized. The binary systems Na-K, Na-S and K-S and the quasi-binary system Na2S-K2S were optimized based on existing experimental data, and the phase relations for the ternary Na-K-S system were predicted based on the thermodynamic properties in binary systems. The liquid model considers two cations, Na+ and K+, and nine anions, S2-, S22-, S32-, S42-, S52-, S62-, S72-, S82- and Va- (charged vacancies as Fcenters for metal solubility). To decrease the amount of independent parameters, the thermodynamic data for the different polysulfide species were fitted as a function of the Gibbs energy of the reaction between liquid alkali sulfide (Na2S or K2S) and liquid
29

sulfur. No reliable thermodynamic data for pure (stoichiometric) polysulfide species exist as molten alkali polysulfides are mixtures of many polysulfide species. The largest polysulfide species in the model is S82-, as molten sulfur, which mainly exists as S8-rings or smaller ring- or chain units, is expected to be depolymerized and broken to ionic polysulfide chains by the addition of alkali metals [61]. The model is not restricted to polysulfides up to S82, but the concentration of possible higher polysulfide units is expected to be very low and was therefore omitted from the present work. Possible branched polysulfide units could exist, but experimental data have shown that the polysulfide ions are predominantly unbranched chains, and therefore branched polysulfide isomers are not taken into consideration here. The existence of polysulfide radical anions has been shown (S2-, S3-, S4-, S6-) [61] but they were not considered in the present assessment. The thermodynamic data for the pure liquid alkali polysulfide components were optimized and fitted as G(M2S1+n) = A(n)+B(n)T (n=1-7) for the reaction M2S(l) + n S(l) M2S1+n(l), M=Na, K. [Eq. 3.36]
The thermodynamic data for M2S(l) and S(l) are given in Appendix A and the thermodynamic data for the polysulfide species were optimized. It was shown that G(M2S1+n) for both Na and K could be represented by the empirical equation
o o o GM 2 S1+n = GM GM n GS (l ) = 2 S1+ n ( l ) 2 S (l )
n A0 + 2 n A1 2 k (k 1) + n B T
k =1
[Eq. 3.37] As can be seen from Equation 3.37, the liquid model parameters are the three values of A0, A1 and B for the Na-S system, the three similar parameters for the K-S system, the excess Gibbs energy parameters of the Na-K system and the S2--Va- interaction parameters for the Na-Na2S and K-K2S liquid regions. A parameter for Na2S-Na2S2 interactions was also included for a better agreement of the Na2S-liquidus line with the experimental data. The thermodynamic properties of three solid solutions were also modeled, the NaK alloy with body-centred cubic structure, cubic Na2S-K2S, and Na2S2-K2S2. The thermodynamic properties for the Na-K alloy were based on a previous assessment by 30

Bale [91]. Very limited experimental data exist for the alkali sulfide and alkali disulfide solid solutions, and only tentative thermodynamic properties were modeled in the present work.
3.5.1.1 Na-S
The phase diagram has been measured by visual-polythermal methods [66], thermal analysis [63-66], differential thermal analysis [60, 66, 68], quenching techniques [66] and EMF-studies [67, 69]. Due to experimental difficulties, a notable scatter exists for different experimental investigations. The main uncertainties stem from difficulties in synthesizing pure samples of sodium sulfide and polysulfides, as hydration or oxidation of the samples easily occur, and due to the fact that sodium polysulfide melts can easily be supercooled and are glass-forming. Tegman [70, 71] and Cleaver and Davies [72] used transpiration techniques to investigate the equilibrium between sulfur gas and sodium polysulfide melt. Maiorova et al. [69], Cleaver and Davies [72] and Gupta and Tischer [67] used EMF-techniques to measure the activity of liquid sulfur in sodium polysulfide melts. Gupta and Tischer [67], Maiorova et al. [69], Morachevskii [73] and Morachevskii et al. [74] measured the activity of liquid sodium in sodium polysulfide melts up to the region of two liquid phases (Sodium polysulfide/sulfur) with EMFtechniques. Based on the recommendations by Sangster and Pelton [87], the most weight was put on the measurements by Rosn and Tegman [66], which is the most complete study of the phase diagram. Rosn and Tegman mainly used high-temperature microscopy, but complementary experiments using thermal analysis, differential thermal analysis and quenching techniques showed good agreement with the high-temperature microscopy. No solid solubility has been reported in the system and no measurements have been made for x(Na) > . Based on the experiments by Dworkin and Bredig [76] on the phase relations of K-K2S, which show the existence of liquid-liquid immiscibility, a miscibility gap might be expected to exist at compositions with x(Na) > . At high sulfur compositions
31

liquid-liquid immiscibility occurs between liquid polysulfide and almost pure liquid sulfur [60, 64, 66, 67]. The Gibbs energy of the liquid sodium polysulfide components from Na2S2 to Na2S8 was optimized and the thermodynamic data of the reaction Na2S(l) + n S(l) Na2S1+n(l) were fitted to the following empirical equation:
o o o 1 GNa 2 S1+ n /( J mol 1 ) = GNa /( J mol 1 ) GNa /( J mol 1 ) n GS ( l ) /( J mol ) = 2 S1+ n ( l ) 2 S (l )
[Eq. 3.38]
48116 n + 2 n 25104 2 k (k 1) + 4.184 n (T / K )

k =1
[Eq. 3.39]
o o The terms GNa and GS ( l ) are found in Appendix A by integrating the Cp expression for 2 S (l )
o H and S using H o f , 298 and S 298 . According to Eq. 3.39, it is assumed that Cp of
formation of liquid polysulfides from liquid S and liquid Na2S is zero. One small additional parameter was added to refine the fit of the Na2S liquidus. According to Sangster and Pelton [87], it is likely that a miscibility gap will be present for liquid Na-Na2S close to the melting point of Na2S. A mixing model parameter was estimated to obtain a miscibility gap of reasonable size. Miscibility gaps in K-KX (X=Cl, Br, I, F, H) systems were observed to generally be smaller than the corresponding Na-NaX gaps [92, 93]. Hence the proposed calculated miscibility gap is larger than the one calculated for the K-K2S system. The proposed miscibility gap is reproduced by using a binary excess parameter, which is given in Appendix C. The calculated phase diagram of Na-S is shown in Figure 3.2. The calculated reverse solubility of liquid S in the polysulfide melt is probably a model artifact due to a limited number of polysulfide species (n=8 is maximum for Na2Sn). The simple temperature dependence of the Gibbs energy of formation of the polysulfides (Eq. 3.39), which was introduced for reasons of simplicity, might also be a cause for the calculated reverse solubility.
32

3.5.1.2 K-S
The phase diagram has been measured by thermal analysis [64, 75, 76], differential scanning calorimetry (DSC) [77, 78] and EMF methods [79, 80]. No solid solubility has been reported for any compounds in the system. Crosbie [79] and Morachevskii et al. [80] used EMF-techniques to measure the activity of liquid potassium in potassium polysulfide melt up to the region of two liquid phases (potassium polysulfide/sulfur). The experimental difficulties for potassium sulfide and polysulfides are similar as in the sodium systems. The phase diagram has been investigated in the whole compositional range and there exists liquid-liquid immiscibility both at the sulfur-rich end with molten sulfur in equilibrium with a potassium polysulfide melt [79, 80], and at the potassium-rich end at compositions with x(K) > [76]. The Gibbs energy of the liquid potassium polysulfide components from K2S2 to K2S8 was optimized and the thermodynamic data of the reaction K2S(l) + n S(l) K2S1+n(l) were fitted to the following empirical equation:
1 o o o GK 2 S1+n /( J mol 1 ) = GK /( J mol 1 ) GK /( J mol 1 ) n GS ( l ) /( J mol ) = 2 S1+ n ( l ) 2 S (l )
[Eq. 3.40]
79496 n + 2 n 41840 2k (k 1) + 1.6736 n (T / K )

k =1
. [Eq. 3.41]
To reproduce the liquidus in the compositional range of K-K2S, the interaction between metallic potassium (nominally K(+)Va(-)) and K2S was optimized. The interaction parameters are given in Appendix C. The calculated phase diagram of the K-S system is shown in Figure 3.2.
3.5.1.3 Na-K
The phase diagram of Na-K has been assessed previously by Bale [91]. In his assessment, Bale [91] used the experimental phase diagram points from Ott et al. [81]; hence the same
33

experimental points were used in the present evaluation. The activity of K in the liquid has been measured by Lantratov [82] at 450C and 500C and by Cafasso et al. [83] at 111C. The enthalpy of mixing of the liquid has been measured calorimetrically by Yokokawa and Kleppa [84] at 111C, and by McKisson and Bromley [85]. Other calorimetric measurements have been done by Douglas et al. [86]: HT-H273.15K for pure K and for a Na-K alloy with 78.26 wt-% K; HT-H323.15K for a Na-K alloy with 53.64 wt-% K and for a Na-K alloy with 44.80 wt.% K. The parameters for the liquid phase and the NaK solid solution (bcc structure) were directly taken from Bale [91]. The calculated phase diagram of Na-K is shown in Figure 3.2.
3.5.1.4 Na2S-K2S
The quasibinary Na2S-K2S system has been studied with DTA by Mkip & Backman [94] and a tentative phase diagram was constructed. They assumed solid solubility for the whole composition range with a minimum solidus temperature at x(K2S)0.65 and 736C. Extensive solid solubility is to be expected as both Na2S and K2S have the same cubic anti-fluorite structure and complete solid solutions in common-anion Na-K salt systems are very common. However, due to the fact that the potassium ion has considerably larger radius than the sodium ion, low temperature miscibility gaps or intermediate phases might occur. Sabrowsky et al. [95] have synthesized the compound KNaS at 600C, and determined the structure of the compound to be hexagonal of PbCl2type, showing the existence of an intermediate phase in the Na2S-K2S system. With no further experimental data existing, ideal behavior was assumed for the liquid phase and the solid solution was modeled as a regular solution with the Compound Energy Formalism (which gives a symmetrical solid-solid miscibility gap). The calculated phase diagram of Na2S-K2S is shown in Figure 3.2.
34
Na - S
1200
1172 C
K-S
1000
Liquid + Gas 948C
1000
Gas + Na2S(s) Liquid + S(l)
800
K2S(s) + Gas Liquid + Gas
800
Liquid
T / (C)
T / (C)
600
Liquid
Liquid 491C K2S 466C Liquid + S(l)
600
Liquid + Na2S(s) Na2S 475 C
Liquid
400
400
Liquid + K2S(s)
284 C 244 C Na2S2 Na2S4 Na2S5
Liquid + S(l)
272C
K2S2
200
98 C
Na2S5(s) + S(l)
200
63 C
255C 127C K2S3
209C K2S6(s) + S(l) K 2 S5 K2S6 K 2 S4
0 0.0
Na(s) + Na2S(s)
0 0.4
K(s) + K2S(s)
0.2
x(S)
0.6
0.8
1.0
0.0
0.2
0.4
x(S)
0.6
0.8
1.0
Na - K
120 100 80 1200
Na2S - K2S
97.2C
1100
T / (C)
40
bcc
20 0 -20 0.0 0.2
bcc + liq. 6.9C bcc + liq. bcc -12.6C Liq. + Na2K bcc + Na2K 0.4 0.6 Na2K + bcc
T / (C)
60
63.2C
Liquid
1000
Liquid
900
800
734 C
700
(Na,K)2S(s.s.)
600 1.0 0.0 0.2 0.4
x(Na)
0.8
x(Na2S)
0.6
0.8
1.0
Figure 3.2. Calculated phase diagrams of Na-S, K-S, Na-K and Na2S-K2S at a pressure of 1 bar shown together with experimental data. References to the experimental data are given in reference [96] (Publication III). 3.5.1.5 Na2S-K2S-S
The phase diagram for the Na-K-S system has not been reported. The only existing phase diagram data in the ternary system is the Na2S-K2S section. The calculated liquidus projection of Na2S-K2S-S is shown in Figure 3.3. No ternary liquid parameters were used for the liquid and no stoichiometric ternary compound was considered in the calculations. Solid Na2S2 and K2S2 have the same crystal structure, and it was assumed that a solid solution is formed. No experimental data exist, and therefore an interaction parameter identical to the parameter of the alkali sulfide solid solution was used. Apart from the (Na,K)2S and the (Na,K)2S2 solid solutions, no solid solubility in higher polysulfides was
35

assumed for the calculation of the liquidus projection shown in Figure 3.3. As Na-K salt solid solutions very often exhibit some solubility, it is possible that at least limited solubility exists. However, due to the low melting point of the compounds and the estimated positive mixing parameter for the solid solutions, this assumption is probably reasonable. The lowest eutectic temperature is 73C at x(S)=0.733, x(Na2S)=0.062 and x(K2S)=0.205.
S
Two liquids
0.9 0.1
0.7
Na2S5 Na2S4
0.6
0 25
0 0 20 15
K2S6 K2S5 K2S4

0.3
0.8
0.2
400
35 0
300
K2S3
0.4
45 0
Na2S2
0.4
0.5
45 0
0 30 0 35 0 40
K2S2
0.6
0.5
650 0 70
50 0
0 75
0.3
0 60
70 0
0 80 0 85
0.7
0.2
65 0
90 0
0.8
95 0
0.1
80 0
75 0
10 00
0.9
Na2S
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
8 90 50 0
1050
Figure 3.3. Calculated liquidus projection of Na2S-K2S-S. Isothermal lines are calculated at 50C intervals.
3.5.2 The Na+,K+/CO32-,SO42-,Cl-,S2-,S2O72- system
1100
mole fraction
K2S
3.5.2.1 Binary systems
All common-cation and common-anion binary systems of the multicomponent Na+,K+/CO32-,SO42-,Cl-,S2-,S2O72- system that were evaluated and optimized in this study
36

are briefly discussed in the following sections. The Na2S-NaCl system has not been reported in the publications, which the present study is based on, but the system is discussed in this section. All optimized interaction parameters for the solid solutions and liquid phase are given in Appendices B and C.
3.5.2.2 Na2CO3-Na2SO4
The phase relations in the Na2CO3-Na2SO4 system has been measured by thermal analysis [97-99], visual-polythermal methods [100] and electrical conductivity measurements [97]. The solid-liquid equilibrium is shown to have a minimum in the solidus and liquidus, with a single solid solution in equilibrium with the liquid phase [97101]. The reported subsolidus phase relations are very complex [98, 99, 102], with the existence of several solid solutions and intermediate phases. The activity of Na2CO3 in the high-temperature hexagonal solid solution was measured by Mukhopadhyay and Jacob [103] with EMF-techniques in the temperature range of 600 to 800C. Flood et al. [104] measured the oxygen activity in liquid Na2CO3Na2SO4 with a controlled level of CO2 in the gas phase. The liquid contains a very small amount of O2- that stems from decomposition of Na2CO3. The study showed that the liquid phase has ideal, or close to ideal, mixing behavior. Based on the measurements, Mukhopadhyay and Jacob [103] derived the excess Gibbs energy of the solid solution using a subregular solution model. In the present study the solution properties of the hexagonal solid solution were taken from the work of Mukhopadhyay and Jacob [103]. A full assessment of the low-temperature phase equilibrium was not performed as the lack of thermodynamic data of the intermediate phases, together with the complex and diverging phase relations reported by Khlapova [98], Kurnakov and Makarov [99] and Makarov and Krasnikov [102], do not allow for a reliable description of the thermodynamic properties for all the low-temperature phases. Only tentative thermodynamic parameters for the Na2SO4-rich and Na2CO3-rich lowtemperature solid solutions are given in Appendix B. The Gibbs energy for the formation of the binary quadruplet in the liquid phase was optimized based on the reported liquidus
37

and solidus data [97, 100, 101] with the most emphasis on the work of Gitlesen and Motzfeldt [97]. The calculated minimum melting point is at x(Na2CO3)=0.63 and 826C. The calculated phase diagram of Na2CO3-Na2SO4 is shown in Figure 3.4.
3.5.2.3 Na2CO3-Na2S
The phase diagram of Na2CO3-Na2S has been measured with thermal analysis [105-108], visual-polythermal methods [107, 109] and high-temperature X-ray powder diffraction [109]. Courtois [108], Tammann and Oelsen [105], and Ovechkin et al. [106] described the system as a simple eutectic system, while Tegman and Warnqvist [107], and Rberg et al. [109] showed the existence of a Na2CO3-rich solid solution in equilibrium with the liquid phase. The experimental scatter in the studies is probably due to impurities in the sodium sulfide, oxidation of the sodium sulfide during the experiments and decomposition of the sodium carbonate. For the optimization in the current study, the most weight was put on the works by Ovechkin et al. [106], Tegman and Warnqvist [107], and Rberg et al. [109]. The thermodynamic data of pure Na2S in the metastable hexagonal structure was modeled based on the subsolidus equilibrium between the hexagonal solid solution and solid Na2S measured by Rberg et al. [109]. No binary interaction parameters for the hexagonal solid solution in the Na2CO3-Na2S system were required to reproduce the experimental data (Henrian ideal mixing was assumed). The calculated eutectic point is at x(Na2S)=0.39 and 761C. The calculated phase diagram of Na2CO3-Na2S is shown in Figure 3.4.
3.5.2.4 Na2SO4-Na2S
The phase diagram of the Na2SO4-Na2S system has been investigated by thermal analysis [105, 110-112], thermogravimetry [112], differential thermal analysis [113] and visualpolythermal methods [113, 114]. EMF-studies have also been conducted for measuring the activity of O2 in equilibrium with solid Na2S and Na2SO4 [115]. The studies indicate that the system is eutectic, with a close agreement of the eutectic temperature at 74038

750C in the different studies, but with highly varying eutectic compositions and liquidus temperatures. The notable scatter in the experimental results is most likely due to difficulties in synthesizing Na2S of high purity and also due to the possible oxidation of Na2S during the experiments. Tran and Barham [112] argued for the existence of partial solid solubility of Na2SO4 in Na2S. However, the method used by Tran and Barham [112] should be considered unreliable due to possible contamination of hydrogenated species, as H2 was used in the experiments. An intermediate solid phase, Na2SO3 (sodium sulfite), has been shown to exist. However, this phase is metastable and decomposes to Na2SO4 and Na2S. Foerster and Kubel [116] and Rberg [114] studied the decomposition of Na2SO3 at high temperatures and both showed that the decomposition is sluggish up to about 600-700C. Rberg [114] also measured the metastable phase diagram for Na2SO4-Na2S with Na2SO3 in the starting material. Solid Na2SO3 was never formed when the sample was cooled from a completely liquid phase. The thermodynamic data of both Na2SO3 and K2SO3 measured by OHare et al. [117] also suggest that the alkali sulfites should decompose to their corresponding alkali sulfates and sulfides. No solid solubility of Na2S in Na2SO4 has been recorded, but the limiting slope of the Na2SO4-liquidus indicates that a solid solution might exist. Na2S is partially soluble in the hexagonal, high-temperature Na2CO3 [109], and the hexagonal, high-temperature forms of Na2CO3 and Na2SO4 show complete solid solution [97, 103]. K2S is also partially soluble in hexagonal K2SO4. This indicates that partial solubility of Na2S in Na2SO4 is plausible. It was therefore assumed that Na2S is soluble in solid hexagonal Na2SO4. The thermodynamic data of pure Na2S in the metastable hexagonal structure is based on the optimization of the Na2S-Na2CO3 system, assuming no additional binary interaction parameters for the Na2S-Na2SO4 system (Henrian ideal mixing is assumed). Due to the large scatter of the experimental phase diagram data, the liquid phase parameter was optimized as a composition- and temperature-independent parameter. The main emphasis was to reproduce the eutectic temperature, which is similar in most of the experimental work. The calculated eutectic point is at x(Na2S)=0.38 and 741C. The calculated phase diagram of Na2SO4-Na2S is shown in Figure 3.4.
39
Na2CO3 - Na2SO4
900 1200 880
Na2S - Na2CO3
Liquid
1000
Liquid Liquid + Na2S(s)

Na2(CO3,S) (hexagonal ss)
T /(C)
860
840 600 820
T/(C)
800
Na2(CO3,S)(hexagonal ss) + Na2S(s)
Na2(CO3,SO4) (hexagonal ss)

400 0.0 0.2 0.4
800
x(Na2CO3)
0.6
0.8
1.0
0.0
0.2
0.4
x(Na2S)
0.6
0.8
1.0
Na2S - Na2SO4
1100 700
Na2SO4 - Na2S2O7
Na2SO4(s,1) + Gas Liquid + Gas
600
Liquid
T / (C)
T /(C)
900
Liquid+Na2S(s)
Na2(SO4,S)(hexa ss)
Liquid
500
Na2SO4(s,1) + Liquid
700
Na2(SO4,S)(hexagonal ss)+Na2S(s)
400
Na2SO4(s,1) + Na2S2O7(s)
300 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
500 0.0
x(Na2S)
x(Na2SO4)
Figure 3.4. Calculated phase diagrams of Na2CO3-Na2SO4, Na2S-Na2CO3, Na2S-Na2SO4 and Na2SO4-Na2S2O7 at a pressure of 1 bar shown together with experimental data. References to the experimental data of the Na2SO4-Na2S2O7 system are given in reference [118] (Publication IV), and for the other systems in reference [119] (Publication V).
3.5.2.5 Na2SO4-Na2S2O7
The phase diagram of the Na2SO4-Na2S2O7 system has been measured by thermogravimetric and visual polythermal studies [120, 121] and thermal/chemical analysis [122]. The equilibrium between a molten mixture of Na2SO4 and Na2S2O7 and gaseous SO3 (including SO2 and O2) has been studied by thermogravimetry [120, 121, 123] and vapor pressure measurements [124]. Additional studies on the high-temperature stability of Na2S2O7 have been made using thermogravimetry [125-127].
40

Tran et al. [125] and Kostin et al. [126, 127] suggested the existence of intermediate solid phases in the system, but this has not been corroborated by other studies. Additionally, both Tran et al. [125] and Kostin et al. [126, 127] used Na2S2O7 containing considerable amounts of impurities, which renders their results unreliable. No solid solutions have been reported in the system. The calculated eutectic point is at x(Na2SO4)=0.09 and 395C. The calculated phase diagram of Na2SO4-Na2S2O7 is shown in Figure 3.4.
3.5.2.6 NaCl-Na2SO4
The phase diagram of the NaCl-Na2SO4 system has been measured by thermal analysis [128-132] and visual-polythermal methods [100, 133-138]. It is a simple binary eutectic system with no solid solution or intermediate phases. No measurements of the thermodynamic properties of the liquid phase have been reported. The measured liquidus and solidus temperatures from the experimental studies are in good agreement with each other. The liquid phase parameter was modeled based on the experimental liquidus and solidus data. The calculated eutectic point is at x(Na2SO4)=0.47 and T=626C. The calculated phase diagram of NaCl-Na2SO4 is shown in Figure 3.5.
3.5.2.7 NaCl-Na2CO3
The phase diagram of the NaCl-Na2CO3 system has been measured by thermal analysis [129, 139-141], visual-polythermal methods [100, 142] and hot filament techniques [143, 144]. It is a simple binary eutectic system with no solid solution or intermediate phases. The activity of Na2CO3 in the molten or partially molten NaCl-Na2CO3 mixtures has been measured by Iwasawa et al. [144] using EMF-techniques. The measured liquidus temperatures shows some scatter, but measured or extrapolated eutectic points from the studies are in good agreement. The calculated eutectic point is at x(Na2CO3)=0.45 and T=632C. The calculated phase diagram of NaCl-Na2CO3 is shown in Figure 3.5.
41

3.5.2.8 NaCl-Na2S
The phase diagram of the NaCl-Na2S system has been studied by Shivgulam et al. [145] using thermal analysis. Magnusson and Warnqvist [146] also reported the eutectic temperature of the same system. The system is a simple binary eutectic system. Shivgulam et al. [145] reported a eutectic point at x(Na2S)=0.24 and 712C, and Magnusson and Warnqvist reported a eutectic temperature of 690C. According to Shivgulam et al. [145], the NaCl-Na2S system shows a tendency for liquid immiscibility in the Na2S-rich region. However, a considerable compositional uncertainty is probable for the measured liquidus points due to the volatilization of NaCl at high temperatures, as pure Na2S melts at almost 400C higher temperature than NaCl. A set of optimized liquid phase parameters could not be attained in this work without the use of a large number of parameters or giving the liquid phase unrealistic mixing properties. Assuming an ideal liquid solution will give reasonable predictions of the solidus temperature, eutectic point and of the liquidus temperatures at NaCl-rich compositions measured by Shivgulam et al. [145]. Further experimental studies are needed for a more detailed evaluation of the liquid phase properties in the binary NaClNa2S system. The calculated eutectic point is at x(Na2S)=0.25 and T=709C. The calculated phase diagram of NaCl-Na2S is shown in Figure 3.5.
42

Na2SO4 - NaCl
900 900
Na2CO3 - NaCl
800
800
Liquid
T / (C)
700
Liquid+ NaCl(s)
Liquid+ Na2SO4(s,hexagonal)
T / (C)
Liquid
700
Liquid+NaCl(s)
Liquid+ Na2CO3(s, hexagonal) NaCl(s) + Na2CO3(s, hexagonal)
600 0.0 0.2
NaCl(s) + Na2SO4(s,hexagonal)
0.4
600 0.8 1.0 0.0 0.2
x(Na2SO4)
0.6
0.4
x(Na2CO3)
0.6
0.8
1.0
Na2S-NaCl
1200
Liquid
1000
T/ (C)
800
Liquid+Na2S(s)
Na2S(s)+NaCl(s)
600 0.0 0.2 0.4
x(Na2S)
0.6
0.8
1.0
Figure 3.5. Calculated phase diagrams of Na2SO4-NaCl, Na2CO3-NaCl and Na2S-NaCl at a pressure of 1 bar shown together with experimental data. References to the experimental data of the Na2SO4-NaCl and Na2CO3-NaCl systems are given in reference [147] (Publication VI). The experimental data of the Na2S-NaCl system is from reference [145].
3.5.2.9 K2CO3-K2SO4
The phase relations of the K2CO3-K2SO4 system have been studied with thermal analysis [101, 148, 149], visual-polythermal methods [100] and high-temperature XRD [148]. At high temperatures a solid solution with hexagonal crystal structure exists over the whole compositional range of K2CO3-K2SO4. The equilibrium between the hexagonal solid solution and the liquid phase has a minimum at pure K2CO3. The low-temperature form of K2CO3 has monoclinic crystal structure and forms a partial solid solution with K2SO4 at temperatures below 422C and x(K2SO4)<0.2 [148]. The low-temperature,
43

orthorhombic K2SO4 forms an extensive solid solution with K2CO3 with a maximum thermal stability at around x(K2SO4)=0.5 and 635C [101, 148]. The activity of K2CO3 in the high-temperature hexagonal solid solution was measured by Mukhopadhyay and Jacob [150] with EMF-techniques in the temperature range of 652 to 892C. Based on the measurements, Mukhopadhyay and Jacob [150] derived the excess Gibbs energy of the solid solution using a subregular solution model. No experimental data on the thermodynamic properties of the liquid phase has been reported. In the present work the solution properties of the hexagonal solid solution were taken from the work of Mukhopadhyay and Jacob [150], and the thermodynamic data for the liquid phase and the monoclinic and orthorhombic solid solutions were derived from the thermodynamic optimization. The study by Barde et al. [149] was considered the most reliable on the solid-liquid equilibrium as they performed the experiments in CO2, thus minimizing the possible decomposition of K2CO3. Therefore, the most weight was put on the work by Barde et al. [149] for the optimization of the liquid phase parameters. The calculated phase diagram of K2CO3-K2SO4 is shown in Figure 3.6.
3.5.2.10 K2CO3-K2S
The phase diagram of K2CO3K2S has been measured by visual-polythermal methods [151], thermal analysis [152] and X-ray diffraction [152]. Ovechkin et al. [152] suggested that the system exhibits full solid-solid miscibility, while the liquidus measurements by Babcock and Winnick [151] indicates that the K2CO3-K2S system is a eutectic system. The two experimental determinations are highly divergent, and both reported melting temperatures of K2S lower than the value used in this work (948C), which is based on the study by Dworkin and Bredig [153]. Babcock and Winnick [151] reported that the K2S used in their experiments contained polysulfides as impurities. The assumption of a complete solid solution reported by Ovechkin et al. [152] is most likely incorrect as K2S and the high-temperature form of K2CO3 have different crystal structures. K2S has cubic crystal structure, while high-temperature K2CO3 has a hexagonal crystal structure. Due to
44

the two strongly diverging experimental determinations of the K2CO3-K2S phase diagram, only tentative thermodynamic parameters were optimized for the liquid phase and solid solutions. Based on the fact that K2S is also partially soluble in hexagonal K2SO4 and Na2S in hexagonal Na2CO3, it was assumed that K2S is partially soluble in hexagonal K2CO3. The thermodynamic data of pure K2S in the metastable hexagonal structure is based on the optimization of the K2SO4-K2S system, assuming no additional binary interaction parameters for the K2CO3-K2S system (Henrian ideal mixing was assumed). Due to highly diverging experimental data, only a tentative composition- and temperature-independent parameter for the liquid was optimized. The most weight was put on the experimental data at K2CO3-rich compositions. The calculated eutectic point is at x(K2S)=0.53 and 641C. The calculated phase diagram of K2CO3-K2S is shown in Figure 3.6.
3.5.2.11 K2SO4-K2S
The phase diagram of K2SO4-K2S has been measured by thermal analysis [154] and by thermogravimetry [155]. Goubeau et al. [154] reported solid solubility of K2S in K2SO4 and the presence of an intermediate phase K2SO (=K2SO43K2S). Winbo [156] confirmed the existence of the intermediate phase by XRD, and also identified the solid solution. However, the crystal structure of the solid solution was found to be orthorhombic, similar to low-temperature, orthorhombic K2SO4(s,), instead of the high-temperature, hexagonal K2SO4(s,), which would be expected from the measured phase diagram of Goubeau et al. [154]. Winbo [156] made the crystallographic determinations on quenched samples from the EMF-experiments. So and Barham [155] reported terminal solid solubility in both K2S and K2SO4, but they found no intermediate phase. However, their study should be considered unreliable due to the possible contamination of hydrogenated species as H2 was used for reducing K2SO4. Winbo [156] measured the activity of O2 in the K2SO4-K2S system using EMF-techniques. The experiments were performed with the K2SO4-rich solid solution at x(K2SO4)=0.75 and with a mixture of K2S and K2SO. The thermo-
45

dynamic properties for solid K2SO3 have been measured by OHare et al. [117], but the phase is a metastable phase which decomposes to K2S and K2SO4. The experimental phase equilibrium data and the existing thermodynamic data are highly contradicting, and reasonable convergence of all existing data could not be obtained in this study. The method used by So and Barham [155] is not a standard method, and the results are considered to be unreliable. The K2S used in the study by Goubeau et al. [154] had up to 3-4% of impurities, mainly in the form of K2SO4, K2SO3 and K2S2O3. Therefore, the mixtures in the experiments by Goubeau et al. [154] have compositional uncertainties, especially in the K2S-rich region. The melting point of K2S in the study by Goubeau et al. [154] was reported to be 912C, compared to 948C reported by Dworkin and Bredig [153], which is the value reported in the NIST-JANAF compilations [52]. This also indicates the existence of impurities in the K2S. The existence of the intermediate phase K2SO has been corroborated, but the experimental data [154, 156] are highly contradicting regarding equilibrium involving the intermediate phase K2SO. A consistent set of thermodynamic data where K2SO was included could not be produced. Only a tentative optimization was made of the K2SO4-K2S system, mainly based on the solidus and liquidus of the K2SO4-rich solid solution from Goubeau et al. [154] and on the EMF-measurements by Winbo [156]. The intermediate phase K2SO was not included in the optimization, and the K2SO4-rich solid solution was considered to have the hexagonal crystal structure. The calculated eutectic point is at x(K2S)=0.63 and 645C. The calculated phase diagram of K2SO4-K2S is shown in Figure 3.6.
3.5.2.12 K2SO4-K2S2O7
The phase diagram of K2SO4-K2S2O7 has been measured by thermal analysis/chemical analysis [122, 157], visual polythermal/thermogravimetric studies [120], EMF-studies [158, 159], and cryoscopy [158]. The equilibrium between a molten mixture of K2SO4 and K2S2O7 and gaseous SO3 (+ SO2 and O2) has been studied by thermogravimetry [120, 121, 160] and EMF-techniques [157, 161]. Kostin et al. [126, 127] reported the
46

existence of the intermediate phases K2SO42K2S2O7 and 2K2SO4K2S2O7 based on thermogravimetric experiments of the decomposition of K2S2O7. No solid solutions have been reported in the system. Kostin et al. [122, 126, 127, 160] used K2S2O7 containing considerable amounts of impurities, which renders their results unreliable. The two reported intermediate phases, K2SO42K2S2O7 and 2K2SO4K2S2O7, were not included in the present optimization due to the lack of any thermodynamic data of these phases and due to the probable impurities in the K2S2O7 in the experiments by Kostin et al. [162]. The calculated eutectic point is at x(K2SO4)=0.07 and 406C. The calculated phase diagram of K2SO4-K2S2O7 is shown in Figure 3.6.
3.5.2.13 KCl-K2SO4
The phase diagram of the KCl-K2SO4 system has been measured by thermal analysis [128, 129, 163] and visual-polythermal methods [100, 135, 136, 142, 164-166]. It is a simple binary eutectic system with no solid solution or intermediate phases. No measurements of the thermodynamic properties of the liquid phase have been reported. The experimental studies are in good agreement with each other for the liquidus temperatures for KCl-rich compositions and for the measured or extrapolated eutectic point. The variations in the measured liquidus temperature are larger at K2SO4-rich compositions, possibly due to volatilization of KCl during the experiments. The calculated eutectic point is at x(K2SO4)=0.26 and 690C. The calculated phase diagram of KCl-K2SO4 is shown in Figure 3.6.
3.5.2.14 KCl-K2CO3
The phase diagram of the KCl-K2CO3 has been measured by thermal analysis [129, 140, 141, 167] and visual-polythermal methods [100, 142]. It is a simple binary eutectic system with no solid solution or intermediate phases. No measurements of the thermodynamic properties of the liquid phase have been reported. The calculated eutectic 47

point is at x(K2CO3)=0.38 and 631C. The calculated phase diagram of KCl-K2CO3 is shown in Figure 3.6.
K2CO3 - K2SO4
1100 1000 1050 900
K2S - K2CO3
Liquid
Liquid
T / (C)
T / (C)
1000
800
950
700
K2(CO3,S)(hexagonal ss)
Liquid+K2S(s)
900
K2(CO3,SO4)(hexagonal ss)
600
K2(CO3,S)(hexagonal ss) + K2S(s)

0.2 0.4 0.6 0.8 1.0
850 0.0 0.2 0.4
500
x(K2CO3)
0.6
0.8
1.0
0.0
x(K2S)
K2S - K2SO4
1100 800 1000
K2SO4 - K2S2O7
K2SO4(s,hexagonal) + Gas Liquid + Gas
Liquid
900
700 600
Liquid
Liquid + K2SO4(s,hexagonal)
K2(SO4,S)(hexagonal ss)
T / (C)
800
T / (C)
500 400
Liquid + K2SO4(s,orthorhombic)
700
Liquid+K2S(s)
K2SO4(s,orthrhombic) + K2S2O7(s,high)
300
600 500 0.0
K2(SO4,S)(hexagonal ss) + K2S

200 0.2 0.4
K2SO4(s,orthorhombic) + K2S2O7(s,low)
0.0 0.2 0.4 0.6 0.8 1.0
x(K2S)
0.6
0.8
1.0
x(K2SO4)
K2SO4 - KCl
1100 900 1000
K2CO3 - KCl
Liquid
900
T / (C)
800
Liquid+K2SO4(s, hexagonal)
700
T / (C)
800
Liquid
KCl(s) + K2SO4(s, hexagonal)

600 500 0.0 0.2
700
Liquid+KCl(s)
Liquid+K2CO3(s, hexagonal)
KCl(s) + K2SO4(s,orthorhombic)
0.4
600 0.8 1.0 0.0 0.2
KCl(s) + K2CO3(s, hexagonal)

0.4
x(K2SO4)
0.6
x(K2CO3)
0.6
0.8
1.0
Figure 3.6. Calculated phase diagrams of K2CO3-K2SO4, K2CO3-K2S, K2SO4-K2S, K2SO4-K2S2O7, K2SO4-KCl and K2CO3-KCl at a pressure of 1 bar shown together with experimental data. References to the experimental data of the K2SO4-K2S2O7 system are given in reference [118] (Publication IV), for the K2CO3-K2SO4, K2CO3-K2S and K2SO4K2S systems in reference [119] (Publication V) and for the K2SO4-KCl and K2CO3-KCl systems in reference [147] (Publication VI).
48

3.5.2.15 Na2CO3-K2CO3
The phase equilibrium of the Na2CO3-K2CO3 system has been studied using thermal analysis [139, 140, 168-171], visual-polythermal methods [172, 173] and XRD-analysis [168]. The system has several solid solutions and displays a minimum in the solidus and the liquidus. Andersen and Kleppa [174] measured the enthalpy of mixing of liquid Na2CO3 and liquid K2CO3 at 905C. Niggli [139], Reisman [168], and Andersen and Kleppa [174] performed their experiments in CO2, and therefore they minimized possible decomposition of the carbonates. Makarov and Shulgina [170] and Reisman [168] reported several solid solutions, both K2CO3-rich and Na2CO3-rich partial solid solutions at low temperature and complete solid solubility of the high-temperature, hexagonal Na2CO3 and K2CO3. Both also reported the existence of an intermediate phase with varying composition around x(Na2CO3)=0.5. Dessureault et al. [175] pointed out that the measured phase equilibrium at intermediate compositions between 400 and 600C is not thermodynamically consistent with either the existence of an intermediate phase or a possible miscibility gap. No thermodynamic or crystallographic data of the intermediate phase have been reported, which could aid in the modeling of the phase. Only a tentative optimization was made in this study of the thermodynamic properties of the low-temperature solid solutions. The intermediate phase was not considered due to the lack of reliable data. The interaction parameter of the liquid phase was optimized based on the measured enthalpy of mixing by Andersen and Kleppa [174]. A small compositiondependent parameter was included in the optimization for better agreement with the experimental enthalpy data. For the solid-liquid equilibrium and the subsolidus equilibrium, the most weight was put on the study by Reisman [168] in the present optimization. The experiments were performed in CO2, and both the solidus and the liquidus were measured. However, the other solid-liquid equilibrium determinations are in good agreement with the study of Reisman [168]. The calculated minimum melting point of the system is at x(Na2CO3)=0.59 and 709C. The calculated phase diagram of Na2CO3-K2CO3 is shown in Figure 3.7.
49

3.5.2.16 Na2SO4-K2SO4
The phase equilibrium in the Na2SO4-K2SO4 system has been studied using thermal analysis [128, 129, 176-179], visual-polythermal methods [135, 180] and XRD-analysis [177, 178, 181]. The system has several solid solutions and has a minimum in the solidus and the liquidus. The experimental data for the solidus and liquidus were determined by thermal analysis [128, 129, 176, 177] and by visual-polythermal methods [135, 180]. The phase equilibrium in the subsolidus region has been determined by thermal analysis [128, 176-179] and XRD-analysis [177, 178, 181]. stvold and Kleppa [182] measured the enthalpy of mixing of liquid Na2SO4 and liquid K2SO4 at 1080C with x(Na2SO4)=0.5. The hexagonal solid solution is stable over the whole compositional range at elevated temperatures. Two low-temperature solid solutions with orthorhombic crystal structure exist at the terminal compositions, and the intermediate phase glaserite, K3Na(SO4)2 dissolves considerable amounts of Na2SO4 at elevated temperatures. The orthorhombic and hexagonal solid solutions were modeled with two sublattices, while the glaserite was modeled with three sublattices, where two sublattices represent two different crystallographic sites occupied by the cations. The liquid phase interaction parameter was fitted to the measured enthalpy of mixing by stvold and Kleppa [182]. The calculated minimum melting point of the system is at x(Na2SO4)=0.74 and 834C. The calculated phase diagram of Na2SO4-K2SO4 is shown in Figure 3.7.
3.5.2.17 Na2S2O7-K2S2O7
The phase diagram of Na2S2O7-K2S2O7 has been measured by thermal analysis [183], differential thermal analysis [184] and conductivity studies [185]. The enthalpy of mixing of the Na2S2O7-K2S2O7 liquid phase has been measured at 445C by drop calorimetry [185]. The studies show the existence of the intermediate solid phase KNaS2O7 and of solid solutions in the Na2S2O7-rich and the K2S2O7-rich regions. The liquidus temperatures reported by Gubareva et al. [184] are significantly lower than those reported
50

by Colombier et al. [183] and Rasmussen et al. [185], whose results are consistent with each other. In the present work, the most weight has been put on the results of Colombier et al. [183] and Rasmussen et al. [185]. The Gibbs energy for the formation of the binary quadruplet in the liquid phase was optimized based on the measured enthalpy of mixing of Rasmussen et al. [185]. The K2S2O7-rich solid solution has the structure of K2S2O7 (s,), and no solid solubility of Na2S2O7 in K2S2O7 (s,) was assumed. The K2S2O7-rich and Na2S2O7-rich solid solutions were modeled with two solid sublattices, with Na+ and K+ on the cationic sublattice and S2O72- on the anionic sublattice. The two calculated eutectic points of the system are at x(Na2S2O7)=0.40 and x(Na2S2O7)=0.61 and both at a temperature of 342C. The calculated phase diagram of Na2S2O7-K2S2O7 is shown in Figure 3.7.
3.5.2.18 NaCl-KCl
The optimized solution parameters for the binary system NaCl-KCl have been reported previously [34, 186]. The liquid phase was modeled with the Modified Quasichemical Model in the Quadruplet Approximation [17], and the solid solution of NaCl-KCl was modeled with a substitutional model. A single NaCl-KCl solid solution with a cubic crystal structure is the precipitating phase at the liquidus. The solution parameters of the solid solution are taken from Sangster and Pelton [34], and the parameters of the liquid phase are taken from Chartrand and Pelton [186]. The optimized parameters from these studies were used in the present study and are given in Appendices B and C. The calculated phase diagram is shown in Figure 3.7.
51

Na2CO3 - K2CO3
950 1100 900
Na2SO4 - K2SO4
850
1000
T / (C)
800
750
700 650 0.0 0.2
(Na,K)2CO3(hexagonal ss)
800 0.4 0.6 0.8 1.0 0.0
T / (C)
Liquid
Liquid
900
(Na,K)2SO4 (s,hexagonal)
0.2 0.4 0.6 0.8 1.0
x(Na2CO3)
x(Na2SO4)
Na2S2O7 - K2S2O7
450 900 800
NaCl-KCl
400
Liquid
Liquid
T / (C)
350
(K,Na)2S2O7 (ss) (Na,K)2S2O7 (ss)
T / (C)
700
600
(Na,K)Cl(ss)
300
(K,Na)2S2O7 (ss)+ KNaS2O7(s) (Na,K)2S2O7 (ss) + KNaS2O7(s)
500
250 0.0
K2S2O7 (s2) + KNaS2O7(s)
400 0.6 0.8 1.0 0.0 0.2 0.4
0.2
0.4
x(Na2S2O7)
x(NaCl)
0.6
0.8
1.0
Figure 3.7. Calculated phase diagrams of Na2CO3-K2CO3, Na2SO4-K2SO4, Na2S2O7K2S2O7 and NaCl-KCl shown together with experimental data. References to the experimental data of the Na2CO3-K2CO3 system are given in reference [119] (Publication V) and for the Na2SO4-K2SO4 and Na2S2O7-K2S2O7 systems in reference [118] (Publication IV).
3.5.2.19 Ternary systems
Several ternary systems have previously been studied experimentally. The ternary systems can be divided into common-ion ternary systems and ternary reciprocal systems. In the common-ion systems either an anion or cation is common for all three end-member components, while ternary reciprocal systems consist of two cations and two anions, where the charge balance constrains the mass balance. As only two cations were considered in the present study, no common-anion ternary systems are considered. The common-cation ternary systems that have been studied experimentally are NaCl-Na2CO3Na2SO4, NaCl-Na2CO3-Na2S, Na2CO3-Na2SO4-Na2S and KCl-K2CO3-K2SO4. All other
52

common-cation ternary systems were considered to have no nonideal ternary interactions, as no experimental data was found in the literature for these systems. The extrapolation of the binary interactions in the ternary systems was made using the Kohler approximation [49] for all systems containing only divalent anions. The Kohler/Toop approximation [51] was used for the systems containing the monovalent anion Cl- or the negatively charged vacancy, Va-. The component containing the monovalent anion is considered to be the asymmetric component if the two other components contain divalent anions. For ternary systems containing Cl-, Va- and a divalent anion, the component containing the divalent anion is considered as the asymmetric component. The ternary reciprocal systems must take into account both first-nearest-neighbor and second-nearest-neighbor interactions in contrast to common-ion ternary systems, where only second-nearest-neighbor interactions are taken in to account in the modeling. The ternary reciprocal systems that have been studied experimentally are Na2SO4-K2SO4Na2S2O7-K2S2O7, Na2CO3-K2CO3-Na2SO4-K2SO4, Na2CO3-K2CO3-NaCl-KCl and Na2SO4-K2SO4-NaCl-KCl. The other ternary reciprocal systems were treated as having no nonideal reciprocal interactions.
3.5.2.20 Na2CO3-Na2SO4-Na2S
Solidus and liquidus temperatures of the Na2CO3-Na2SO4-Na2S system have been measured by differential thermal analysis [113]. Andersson [113] reported a minimum melting temperature of 7155C at an approximate composition of x(Na2S)=0.35, x(Na2CO3)=0.20 and x(Na2SO4)=0.45. The experimental points in the binary Na2SNa2SO4 system in the same study show considerable scatter, possibly due to oxidation of Na2S. The reported melting point of Na2S was about 30C lower than the melting point reported in the NIST-JANAF compilations [52]. Andersson [113] reported that the purity of the Na2S sample was higher than 98.3%. No ternary interaction parameters for the liquid phase were used due to the considerable experimental scatter in the binary systems Na2CO3-Na2S and Na2SO4-Na2S, and due to the uncertainties in the determination of the ternary phase diagram [113].
53

The calculated minimum melting temperature of the Na2CO3-Na2SO4-Na2S system is 733C at the composition of x(Na2S)=0.356, x(Na2CO3)=0.308 and x(Na2SO4)=0.336. The calculated liquidus projection of Na2CO3-Na2SO4-Na2S is shown in Figure 3.8. Most calculated solidus and liquidus temperatures are within 20C of the measured values, which is a reasonable agreement, given the experimental scatter in the binary systems Na2CO3-Na2S and Na2SO4-Na2S.
Figure 3.8. Calculated liquidus projection of the Na2CO3Na2SO4-Na2S system. Isothermal lines are calculated at 50C intervals. Precipitating solid phases are Na2S (a) and the hexagonal solid solution, Na2(SO4,CO3,S) (b). The dotted line indicates the maximum solubility of the hexagonal solid solution. The minimum melting point is denoted by the symbol .
3.5.2.21 NaCl-Na2CO3-Na2S
The phase diagram of the NaCl-Na2S-Na2CO3 system has been reported by Warnqvist and Norrstrm [187] and Shivgulam et al [145]. Magnusson and Warnqvist [146] reported a ternary eutectic temperature of 590C. Shivgulam et al [145] reported a
54

eutectic point at x(NaCl)=0.35, x(Na2CO3)=0.62, x(Na2S)=0.03 and a temperature of 598C. Shivgulam et al [145] also reported the measured liquidus temperatures. Due to the high uncertainties in the binary NaCl-Na2S system related to the volatilization of NaCl, the liquidus measurements of Shivgulam et al.[145] must be considered to have a high uncertainty, especially at high concentrations of Na2S. No additional ternary parameters were optimized due to the uncertainties in the binary systems containing Na2S. The calculated ternary eutectic point is at x(NaCl)=0.48, x(Na2CO3)=0.35, x(Na2S)=0.17 and a temperature of 603C.
3.5.2.22 NaCl-Na2CO3-Na2SO4
Bergman and Sementsova [100] measured the liquidus temperature for several sections in the NaCl-Na2CO3-Na2SO4 system using visual-polythermal methods. Based on the measured liquidus temperatures they estimated the minimum melting point of the system to be at the composition of x(NaCl)=0.519, x(Na2CO3)=0.241, x(Na2SO4)=0.241 and at a temperature of 612C. The solidus temperatures were measured for several compositions in this study using simultaneous DTA and TGA [147]. Several cycles were made between temperatures close to the liquidus and solidus in order to homogenize the solid solutions in the samples. The heating and cooling rates were 20C/min, with some runs also conducted with 10C/min. The solidus and liquidus temperatures in the system are reproduced by the thermodynamic model satisfactorily without the use of a ternary interaction parameter. The extrapolation of the binary interaction parameters was made using an asymmetric Kohler/Toop model [188], where NaCl is the asymmetric component. The calculated minimum melting point is at x(NaCl)=0.511, x(Na2CO3)=0.266, x(Na2SO4)=0.224 and a temperature of 612C. Isoplethal sections in the system are shown in Figure 3.9 together with experimental points from Bergman and Sementsova [100] and from this study, and the calculated ternary phase diagram is shown in Figure 3.10.
55
900 850 800 750
900
Liquid
850 800
Liquid
T / (C)
700 650 600 550 500 0.0 0.2
Liquid + Na2(SO4,CO3)(hexa ss)
T / (C)
750 700
Liquid+Na2(SO4,CO3)(hexa ss)
650
NaCl(s) + Na2(SO4,CO3)(hexa ss)
600
NaCl(s)+Na2(SO4,CO3)(hexa ss)
550 0.4
x(Na2CO3)
0.6
0.8
1.0
0.0
0.2
0.4
x(Na2SO4)
0.6
0.8
1.0
Fig 3.9a.
900 850 800
Fig 3.9b
Liquid
T / (C)
750 700 650 600 550 0.0 0.2 0.4
NaCl(s)+Na2(SO4,CO3)(hexa ss)
0.6 0.8 1.0
x(NaCl)
Fig 3.9c Figure 3.9. Calculated isoplethal sections in the NaCl-Na2CO3-Na2SO4 section. a) Na2CO3-(0.67 Na2SO4+0.33 NaCl) b) Na2SO4-(0.6 Na2CO3+0.4 NaCl) c) NaCl-(0.5 Na2SO4+0.5 Na2CO3). Experimental points are from Bergman and Sementsova [100](filled circles) and from this study (Publication VI)(Crosses: thermal peaks; filled diamonds: thermal onset).
56
NaCl
0.9 0.1
0.8
750
0.2
a
700 650
0.7
0.3
0.6
0.4
0.5
0.5
612
0.4
0.6
700
0.3
0.7
0.2
0.8
0.1
b
0.9 0.8 0.7 0.6 0.5
0.9
800
0.4 0.3 0.2 0.1
Na2CO3
mole fraction
Na2SO4
Figure 3.10. Calculated liquidus projection of the NaClNa2CO3-Na2SO4 system. Isothermal lines are calculated at 50C intervals. Precipitating solid phases are NaCl (a) and the hexagonal solid solution, Na2(SO4,CO3) (b). The minimum melting point is denoted by the symbol .
3.5.2.23 KCl-K2SO4-K2CO3
Bergman and Sementsova [100] measured the liquidus temperature for several sections in the KCl-K2CO3-K2SO4 system using visual-polythermal methods. Based on the measured liquidus temperatures they estimated the minimum melting point of the system to be at the composition of x(KCl)=0.630, x(K2CO3)=0.312, x(K2SO4)=0.058 and at a temperature of 622C. The solidus temperatures were measured for several compositions in this study [147] using simultaneous DTA and TGA. Several cycles were made between temperatures close to the liquidus and solidus in order to homogenize the solid solutions in the samples. The heating and cooling rates were 20C/min, with some runs also conducted with 5C/min.
57

The solidus and liquidus temperatures in the system were not reproduced satisfactorily with only binary interaction parameters. Therefore, a ternary parameter was included to give a better prediction of the phase relations. The ternary parameter gives the effect of one component on the interaction parameter for the binary system containing the two other components. The common-cation ternary parameter is given in Appendix C. The extrapolation of the binary interaction parameters was made using an asymmetric Kohler/Toop model [188], where KCl is the asymmetric component. The calculated minimum melting point is at x(KCl)=0.626, x(K2CO3)=0.316, x(K2SO4)=0.058 and a temperature of 628C. The calculated ternary phase diagram is shown in Figure 3.11, and isoplethal sections in the system are shown in Figure 3.12 together with experimental points from Bergman and Sementsova [100] and from this study.
KCl
0.9 0.1
0.8
700
0.2
0.7
a
628
0.3
0.6
0.4
70
0.5
0.5
0.4
80
0.6
0.3
0.7
0.2
0 90
0.8
0.1
0.9
00 10
0.9 0.8 0.7 0.6
K2CO3
mole fraction
0.5
0.4
0.3
0.2
0.1
K2SO4
Figure 3.11. Calculated liquidus projection of the KClK2CO3-K2SO4 system. Isothermal lines are calculated at 50C intervals. Precipitating solid phases are KCl (a) and the hexagonal solid solution, K2(SO4,CO3) (b). The minimum melting point is denoted by the symbol .
58
1100 900
1000
Liquid
900
Liquid
T / (C)
800
Liquid+K2(CO3,SO4)(hexa ss)
700
KCl(s)+K2(CO3,SO4)(hexa ss)
600
KCl(s)+K2(SO4,CO3)(ortho ss)
500 0.0 0.2 0.4 600
T / (C)
800
700
KCl(s)+K2(CO3,SO4)(hexa ss)
0.0 0.2 0.4
x(K2SO4)
0.6
0.8
1.0
x(KCl)
0.6
0.8
1.0
Fig. 3.12a
720
Fig 3.12b
700
680
Liquid
T / (C)
660
640
620 600 0.0
KCl(s)+K2(SO4,CO3)(hexa ss)
KCl(s)+ K2(SO4,CO3)(ortho ss)
0.2
0.4
x(A)
0.6
0.8
1.0
Fig 3.12c Figure 3.12. Calculated isoplethal sections in the KCl-K2CO3-K2SO4 section. a) K2SO4(0.14 K2CO3+0.86 KCl) b) KCl-(0.7 K2CO3+0.3 K2CO3) c) A-B section: A=(0.29 K2SO4+0.71 KCl), B=(0.43 K2CO3+0.57 KCl). Experimental points are from Bergman and Sementsova [100](filled circles) and from this study (Publication VI)(Crosses: thermal peaks; filled diamonds: thermal onset).
3.5.2.24 Na2SO4-K2SO4-Na2S2O7-K2S2O7
The phase equilibrium in the Na2SO4-K2SO4-Na2S2O7-K2S2O7 system has been studied with visual-polythermal methods [120] and by thermogravimetry [121]. In these experiments the liquid phase consists of Na+, K+, SO42- and S2O72-, and is therefore a reciprocal phase. The condensed phases are in equilibrium with the gas phase, which
59

consists of SO2, SO3 and O2. Flood and Frland [121] showed that at specific temperatures and partial pressures of SO3, liquid Na2SO4-Na2S2O7 will be more sulfaterich than liquid K2SO4-K2S2O7. Accordingly, liquid Na2S2O7 will decompose at lower temperatures than K2S2O7. Flood and Frland also showed that in a reciprocal Na+,K+/SO42-,S2O72- liquid, the composition will become more sulfate-rich as Na/(Na+K) increases. The experiments were performed at 662C with controlled SO3 partial pressure. Coats et al. [120] used visual methods to study the formation of a liquid phase for mixtures of Na2SO4 and K2SO4 in contact with a gas containing 200 or 2000 ppm of SO3. They showed that the condensed phases are fully molten at temperatures of 330430C in 200 ppm SO3 and at 330-500C in 2000 ppm SO3. At lower temperatures the solid phases are alkali disulfates (also called pyrosulfate), and at higher temperatures the liquid will decompose to solid alkali sulfates. The liquid phase is a reciprocal Na+, K+/SO42-,S2O72- liquid that is rich in S2O72-. At temperatures above 800C, the solid sulfates will melt and form a liquid that is rich in SO42-. In the present work, no additional reciprocal parameter for the liquid was included, meaning that g NaK / SO4S2O7 = 0 . The Gibbs energy for the reciprocal quadruplets is directly calculated from the Gibbs energy of the unary and binary quadruplets. The phase equilibrium in the multicomponent system is satisfactorily predicted without any additional parameters. The calculated liquidus projection of the reciprocal Na2SO4K2SO4-Na2S2O7-K2S2O7 system is shown in Figure 3.13.
60
K2SO4
0.2 0.4 0.6 0.8
Na2SO4
800
0.8
90 0
0.8
0.6
700
0.6
0.4
0.4
600
0.2
500 b
0.2
0.2
c d
0.4
e
0.6
f
0.8
K 2 S2 O7
KNaS2O7
Na2S2O7
Figure 3.13. Calculated liquidus projection of Na2SO4Na2S2O7-K2SO4-K2S2O7. Isothermal lines are plotted in 50C intervals. The precipitating solid phases in the different phase fields are annotated with a-f. a) Hexagonal (Na,K)2SO4, b) Orthorhombic K-rich (K,Na)2SO4, c) Glaserite, d) K-rich (K,Na)2S2O7 e) KNaS2O7 f) Na-rich (Na,K)2S2O7. Formation of the gas phase is suppressed in the calculations.
3.5.2.25 Na2CO3-Na2SO4-K2CO3-K2SO4
The liquidus temperatures in the reciprocal ternary Na2CO3-Na2SO4-K2CO3-K2SO4 system have been measured by visual-polythermal methods [164, 189, 190]. The hexagonal solid solution is the only solid phase in equilibrium with the liquid phase. Sementsova et al. [190] suggested that the hexagonal solid solution has a miscibility gap, which can be seen from the solid-liquid equilibrium close to the minimum melting
61

temperature of the system. Small composition-independent reciprocal parameters were optimized for both the liquid phase and the hexagonal solid solution. When only one reciprocal parameter was used, either for the liquid phase or the solid solution, poorer agreement with the experimental data was obtained. The calculated minimum melting temperature is 671C at n(SO42-)/(n(SO42-) +n(CO32-))=0.71 and n(Na+)/(n(Na+)+n(K+))=0.60. The calculated liquidus projection of the Na2CO3-Na2SO4-K2CO3-K2SO4 system is shown in Figure 3.14.
Na2SO4
0.2 0.4 0.6 0.8
Na2CO3
0.8
0.8
671 70 0
80 0
90 0
0.6
0.6
0.4
0.4
0.2
0.2
10 00
0.2 0.4 0.6 0.8
K2SO4
K2CO3
Figure 3.14. Calculated liquidus projection of Na2CO3Na2SO4-K2CO3-K2SO4. Isothermal lines are plotted in 50C intervals. The precipitating solid phase is the hexagonal (Na,K)2(CO3,SO4) solid solution. The symbol denotes the composition of the calculated minimum melting temperature in the system.
62

3.5.2.26 NaCl-Na2SO4-KCl-K2SO4
The phase relations in the ternary reciprocal system has been studied with thermal analysis [128-130] and visual-polythermal methods [135, 138, 191]. The different studies give similar results for the liquidus temperature, even though a considerable scatter can be observed. Jnecke [128] reported the (Na,K)Cl solid solution and the hexagonal (Na,K)2SO4 solid solution as the precipitating phases at the liquidus. In contrast, Akopov and Bergman [135] reported a third precipitating phase, and in a later study [138] two additional precipitating phases close to the minimum melting point of the system. The three phases have a maximum thermal stability of about 680 to 730C. Akopov and Bergman [135, 138] did not identify these precipitating phases, but suggested that they might be binary alkali sulfate compounds, either solid solutions or stoichiometric phases. It is not fully clear if the additional phases actually have been identified or if their existence is assumed based on slope changes in the liquidus line of several sections. The existence of a reciprocal solid phase has not been shown. The three unidentified precipitating phases in the studies of Akopov and Bergman [135, 138] are not in agreement with the phase relations in the Na2SO4-K2SO4 system. The exact nature of these phases is not clear, and they are not mentioned in the other studies of this system. The three unspecified phases have not been included in the present optimization of the reciprocal systems, as there is no basis for evaluating their thermodynamic properties. A reciprocal parameter for the liquid phase was optimized for this system. The parameter is given in Appendix C.The calculated minimum melting point in the NaClNa2SO4-KCl-K2SO4 system is at the composition of n(K+)/(n(Na+)+n(K+))=0.384 and n(SO42-)/(n(SO42-)+n(Cl-))=0.389 at a temperature of 517C. The liquidus projection of the system is shown in Figure 3.15.
63
Na2SO4
0.2 0.4 0.6 0.8
K2SO4
90 0
a
60
0.8
0.8
80
70 0
0
0.6
0.6
517
0.4 0.4
0 60
0.2
0.2
0 70
0.2 0.4
0.6
0.8
(NaCl)2
(KCl)2
Figure 3.15. Liquidus projection of the (NaCl)2-(KCl)2Na2SO4-K2SO4 system. Isothermal lines are plotted in 50C intervals. The precipitating solid phases are the hexagonal (Na,K)2SO4 solid solution (a) and the (Na,K)Cl solid solution (b). The minimum melting point of the system is denoted by the symbol .
3.5.2.27 NaCl-Na2CO3-KCl-K2CO3
The liquidus of the NaCl-Na2CO3-KCl-K2CO3 system has been measured using thermal analysis [129, 140, 167, 192-194] and visual-polythermal methods [164, 191, 195]. Solidus temperatures have been measured with thermal analysis [194]. The liquidus temperature on the NaCl-K2CO3 and KCl-Na2CO3 sections shows some variation between the different studies. Differences of up to 60C can be observed in the Na2CO3rich region of the KCl-Na2CO3 section. Similar variations are also observed in the NaCl-
64

Na2CO3 system, suggesting possible experimental difficulties at Na2CO3-rich compositions. The liquidus projection shows that the (Na,K)Cl solid solution and the hexagonal (Na,K)2CO3 solid solutions are the precipitating solid phases. A small reciprocal parameter for the liquid phase was added, mainly on the basis of the liquidus temperatures in the diagonal sections. The reciprocal parameter is given in Appendix C. The calculated minimum melting point in the NaCl-Na2CO3-KCl-K2CO3 system is at the composition of n(K+)/(n(Na+)+n(K+))=0.269 and n(CO32-)/(n(CO32-) +n(Cl-))=0.314 and at a temperature of 565C. The calculated reciprocal liquidus projection is shown in Figure 3.16.
Na2CO3
0.2 0.4 0.6 0.8
K2CO3
0 80
0 70
80
0
0.8
0.8
a
60 0
0 60
0.6
0.6
0.4
565
0 80
0.4
0.2
0.2
0.2
0.4
0.6
0.8
(NaCl)2
(KCl)2
Figure 3.16. Liquidus projection of the (NaCl)2-(KCl)2Na2CO3-K2CO3 system. Isothermal lines are plotted in 50C intervals. The precipitating solid phases are the hexagonal (Na,K)2CO3 solid solution (a) and the (Na,K)Cl solid solution (b). The minimum melting point of the system is denoted by the symbol .
65

3.5.3.28 Multicomponent systems: NaCl-Na2SO4-Na2CO3-KCl-K2SO4-K2CO3
Bergman and Sementsova have measured the liqudus temperature in the multicomponent reciprocal NaCl-Na2SO4-Na2CO3-KCl-K2SO4-K2CO3 system using visual-polythermal methods [142, 164, 191]. The precipitating solid phases are the (Na,K)Cl solid solution and the hexagonal (Na,K)2(SO4,CO3) solid solution. An additional primary precipitating phase at sulfate-rich compositions was proposed by Bergman and Sementsova [142] and Sementsova and Bergman [164]. The phase was not identified but assumed to be an intermediate phase in the Na2SO4-K2SO4 system, either 2Na2SO4K2SO4 or 3Na2SO4K2SO4. A similar phase has been reported by Akopov and Bergman [135, 138] in the NaCl-Na2SO4-KCl-K2SO4 system. A mineral called hanksite has been identified with the chemical composition Na22K(CO3)2(SO4)9Cl [196-199]. Ramsdell [199] concluded that if hanksite is heated it will decompose to a solid solution with a composition of 9Na2SO42Na2CO3 and to KCl before any melting occurs. Correspondingly, hanksite is not a primary precipitating solid phase from a melt with the hanksite composition. The lowest liquidus temperature in the reported sections is 512C [142]. No solidus temperatures have been reported. The calculated liquidus temperatures versus experimental liquidus temperatures from Bergman and Sementsova [142, 164, 191] are shown in Figure 3.17. The thermodynamic properties of the multicomponents liquid phase calculated by the model are obtained solely from binary, ternary, and ternary reciprocal parameters. No additional higher-order parameters are added to the liquid model or the solid solution models. The calculated liquidus temperatures for the multicomponent systems are predictions based on optimizations of the binary and ternary subsystems. The calculated liquidus temperatures are generally in good agreement with the measured liquidus temperatures. The maximum difference between the calculated and experimental liquidus temperatures is about 30C. As no experimental section can be found in more than one study, it is difficult to estimate the experimental error of the studies. However, the temperature measurements at the intersection of the NaCl-K2SO4K2CO3 and KCl-Na2SO4-Na2CO3 systems show differences of up to 20C at specific compositions [191]. As the liquidus temperatures in the NaCl-Na2CO3-KCl-K2CO3 and 66

NaCl-Na2SO4-KCl-K2SO4 systems show experimental variations of 30C or higher, it must be considered that the liquidus predictions of the multicomponent sections are well within the experimental error limits. The lowest calculated melting point of the NaCl-Na2SO4-Na2CO3-KCl-K2SO4K2CO3 system is at a temperature of 501C and a composition of n(K+)/(n(K+)+n(Na+))=0.341, n(SO42-)/(n(SO42-)+n(CO32-)+n(Cl-))=0.294, and n(CO32-)/ (n(SO42-)+n(CO32-)+n(Cl-))=0.132. The solid phases in equilibrium with the liquid phase are the alkali chloride solid solution and the hexagonal alkali sulfate-carbonate solid solution.
1000
900
T(calc.) / C
800
700
600
500 500
600
700
800
900
1000
T (meas.) / C
Figure 3.17. Calculated liquidus temperatures of the Na+,K+/ Cl-,SO42-,CO32- system versus measured liquidus temperatures from Sementsova and Bergman [164] (circles) and Bergman and Sementsova [191] (squares).
67
Chapter 3-Thermodynamic modeling 3.6 Discussion

An extensive thermodynamic evaluation and optimization of the thermodynamic properties of the phases in the Na+,K+/CO32-,SO42-,S2-,S2O72-,Sx2-,Cl-,Va- system was conducted in this study. All possible combinations of binary and higher order systems were not evaluated due to the lack of experimental data. Systems containing alkali sulfides or polysulfides often show considerable scatter in the experimental phase relations due to experimental difficulties. Additionally, considerable uncertainties exist for the low-temperature phase relations involving complex solid solutions. Large uncertainties in the experimental data also give similarly large uncertainties in the thermodynamic descriptions of the phases. However, most experimental measurements of solid-liquid phase equilibrium can be predicted by the obtained thermodynamic database within the experimental uncertainties in these studies. Additional well-defined measurements of thermodynamic properties of the liquid phase and the solid solutions and of the phase relations of the binary and multicomponent systems could contribute to the validation of the present database and would also provide input data for further improvements.
3.7 Conclusions
A critical evaluation of all available thermodynamic and phase diagram data for the NaK-S system and for the Na+,K+/CO32-,SO42-,Cl-,S2-,S2O72- system was performed. The thermodynamic properties of the liquid phase were modeled using the Modified Quasichemical Model in the Quadruplet Approximation. The present database reproduces the solid-liquid equilibrium of the binary, ternary and quaternary systems to within the experimental uncertainties. The database of thermodynamic data for all phases can be used, along with other databases and Gibbs energy minimization software, to calculate the phase equilibria and all thermodynamic properties of multicomponent alkaline salt mixtures, which are of great importance for ash-related problems in biomass combustion and for many chemical processes in black liquor combustion.
68
Chapter 4-Borate autocausticizing 4. Alkali borates in the kraft recovery boiler

In the kraft pulping process, the white liquor is produced by a causticizing process, in which dissolved smelt (green liquor) reacts with lime to form dissolved NaOH and solid CaCO3. The aqueous phase is separated from the lime mud and is used as the pulping agent. The CaCO3 is calcined in a lime kiln to CaO. The main reactions in the causticizing process are given below:
CaO(s) + H2O(l) Ca(OH)2(s) Ca(OH)2(s) + Na2CO3(aq) 2 NaOH(aq) + CaCO3(s) CaCO3(s) CaO(s) + CO2(g)
[Eq. 4.1] [Eq. 4.2] [Eq. 4.3]
The main stages of the chemical recovery in the kraft pulping process are shown in the Figure 4.1.
CaO
Wood Lime Burning Causticizing
Pulping
Na,S Washing
NaOH(aq) Na2S(aq) Na2CO3(aq) Na2S (aq)
Pulp
CaCO3
Dissolving
Na2CO3(l) Na2S (l)
Evaporation Na,S
Burning
Figure 4.1. The chemical recovery cycles in the kraft pulping process, showing the chemicals related to causticizing in different processes in the pulp mill
69
Chapter 4-Borate autocausticizing
The conventional causticizing process using lime is an integral part of the kraft process. However, it has drawbacks in terms of economy, energy economy, efficiency, and fuel consumption. These limitations provided the incentive for development of alternative causticizing processes. In the 1970s, much of the work on alternative causticizing processes was conducted in Finland by Kiiskil [200-206] and Janson [207-214]. There was renewed interest at the end of the 1990s. The main focus has been on reducing the load on the lime cycle; causticizing in pulping processes with low causticizing demand; and eliminating the increased causticizing demand in black liquor gasification technologies.
4.1 Definitions of nonconventional causticizing concepts

The main concept behind the alternative causticizing technologies is to add a compound to the furnace, where it reacts with molten Na2CO3, releasing CO2. Dissolving the resulting smelt in water yields white liquor directly. The alternative causticizing concepts can be divided into two categories based on the water solubility of the reaction product: autocausticizing, and direct causticizing. In autocausticizing, the pulping chemicals causticize themselves during combustion of the black liquor, without the need for addition or removal of causticizing compounds or reaction products [215]. The autocausticized smelt must be water-soluble, and the decarbonating agent or its derivatives travel through the entire pulping and recovery cycle, either as active agents in the pulping process or as inert materia. In direct causticizing, a decarbonating agent is added to the chemical recovery cycle, and the pulping chemicals are causticized in the recovery boiler furnace. The decarbonating agent is regenerated when the smelt is dissolved in a separate process. The decarbonating agent must be insoluble in water, and it is be separated from the aqueous phase as a solid phase. In direct causticizing, the decarbonating agents do not travel through the pulping process. The term in situ causticizing is used as a term to include both autocausticizing and direct causticizing. The term smelt causticizing is used to describe a process in which the decarbonation reactions
70

take place in the recovery boiler smelt. Strictly speaking, the terms autocausticizing and direct causticizing are not included in the term smelt causticizing, but many of the in situ causticizing concepts involve causticizing reactions in the smelt.
4.2 Borate autocausticizing
Jan Janson [207-214] proposed an alternative chemical pulping process in the 1970s, in which the pulping chemicals (or portions of them) would also act as decarbonating agents for the Na2CO3 formed in the recovery boiler during the traditional kraft process. The addition of lime or other chemicals to the green liquor are not required as, ideally, the green liquor is identical to the white liquor. Janson carried out an extensive study to find suitable chemicals that would form sufficiently alkaline solutions for effective pulping, which would also serve as effective decarbonating agents in the recovery boiler furnace. The chemicals investigated were B2O3, P2O5, SiO2, and Al2O3, or sodium salts of these oxides [207, 211]. The principle behind autocausticizing can be illustrated by the general reactions given below, where X represents an above-mentioned oxide: Pulping: NaOH(aq) + Org-H Org-Na + H2O(l) Combustion: Org-Na Na2CO3(s,l) Decarbonation of smelt: n X(s,l) + Na2CO3(s,l) Na2XnO(s,l) + CO2(g) Dissolving of smelt/formation of pulping agents: Na2XnO(s,l) + H2O(l) 2 NaOH(aq) + n X(aq). [Eq. 4.7] [Eq. 4.6] [Eq. 4.5] [Eq. 4.4]
The formation of Na2CO3 during the combustion of black liquor (Eq. 4.5) can also be inhibited by the presence of the causticizing chemicals, if the organically bound sodium reacts with the causticizing chemicals instead of forming Na2CO3. 71

Several problematic aspects were encountered with many of the compounds studied. The compound Na4P2O7, sodium diphosphate, was shown to have good decarbonating ability, but the dissolved salts were not sufficiently alkaline to be utilized in the normal kraft process. The compounds Na2Si2O5 and Al2O3 were shown to be associated with the precipitation of solids from alkaline solutions, which in practice could cause severe problems with scaling on evaporator surfaces. According to Jansons studies [207-214], the most promising compounds for autocausticizing are sodium borates. The compound NaBO2 was shown to be a suitable decarbonating compound which also yields pulping liquors of acceptable quality. The main reactions for the autocausticizing concept proposed by Janson are the following: Decarbonation of smelt: 2 NaBO2(s,l) + Na2CO3(s,l) Na4B2O5(s,l) + CO2(g)
B
[Eq. 4.8]
Dissolving of smelt/formation of pulping agents: Na4B2O5(s,l) + H2O(l) 2 NaOH(aq) + 2 NaBO2(aq).

B
[Eq. 4.9]
A schematic diagram of the borate autocausticizing applied to the kraft pulping process is given in Figure 4.2.
Wood
NaBO2(aq) NaOH(aq) Na2S (aq)
Pulping
Na, S, B
Pulp Washing
Dissolving
Na4B2O5(l) Na2S (l)
Evaporation
Na, S, NaBO2(aq)
Burning
Figure 4.2. Full borate autocausticizing applied to the kraft pulping process according to Janson [207-214], showing the borate speciation at different stages
72
Janson studied the use of borates in both kraft pulping and alkali pulping. Janson and Pekkala [208-210] replaced one mole of NaOH by one mole of Na2HBO3 and found no significant differences in the degree of delignification of the wood or mechanical properties of the pulp in alkali cooking, oxygen alkali cooking and bleaching, or kraft cooking. The term Na2HBO3 is used in a nominal sense, as in reality it was a mixture of NaOH and NaB(OH)4 (or NaBO22H2O) with an overall Na/B ratio of 2. The exact speciation of the borates in a solution with an Na/B ratio of 2 is uncertain due to the complex aqueous chemistry of borates. The results of Janson and Pekkala [208-210] suggest that with the use of Na2HBO3 (=NaOH + NaBO2), the borate component has neither a positive nor a negative effect on the cooking and bleaching. The borate-containing black liquors had considerably lower heating values on a dry solids basis compared to the borate-free black liquors due to the higher content of inorganic salts. The endothermic decarbonation reactions will also reduce the heating value of the black liquor if the reactions occur. Janson [209] measured the viscosity of borate-containing and borate-free black liquors from kraft pulping. He found no difference between the viscosity of borate-containing and borate-free liquors from birch, but borate-containing black liquors from pine had higher viscosities than borate-free liquors at fixed dry matter contents. Janson also studied the autocausticizing reactions of sodium compounds as a function of temperature and Na/B ratio using various gas compositions (N2 or N2/CO2 mixtures) [211]. Organic compounds were added in some experiments to investigate the reactions in synthetic black liquor from an alkaline cooking process. The results showed that decarbonation was more or less complete when Na/B<2. Carbonate was retained in the reaction products at higher Na/B ratios. The decarbonation reactions were inhibited in experiments with high CO2 content in the gas phase, which is to be expected based on equilibrium considerations of the autocausticizing reaction (Eq. 4.8). Experiments with kraft black liquors and with mixtures of Na2CO3, Na2S, sodium borates, and organic compounds showed that sulfur has no significant effect on the autocausticizing reactions [212].
73

A full-scale plant trial of borate autocausticizing was carried out at the Enso Gutzeit liner board mill in Kotka, Finland from 1981-1982. The results were inconclusive, and the mill trials were discontinued. Grace [216] suggested that full-scale implementation of borate autocausticizing is technically difficult. The high amount of borate in the liquor cycle, low heating values and high viscosity of borate-containing black liquor, the need for auxiliary fuels, and the cost of make-up chemicals are the most serious issues limiting the full-scale application of borate autocausticizing.
4.2.1 Partial borate autocausticizing
At the end of the 1990s, there was a renewed interest in borate autocausticizing. Tran et al. [217] suggested that partial autocausticizing using borates could be an attractive alternative for reducing the use of lime in the causticizing cycle. In the partial autocausticizing concept, less borate is used than in the autocausticizing concept of Janson, and the Na2CO3 is only partially decomposed in the recovery boiler. The remaining Na2CO3 is causticized in the conventional manner. This reduces the amount of borates in the liquor cycle, and lessens the effect of borates on the heating value and viscosity of the black liquor. Partial autocausticizing is of interest mainly to pulp mills where causticizing is a limiting factor in pulp production. Nonconventional causticizing concepts, including partial borate autocausticizing, are of interest to pressurized black liquor gasification technologies, as more Na2CO3 is formed during black liquor conversion under pressurized conditions than under atmospheric conditions. Tran et al. [217] studied the reactions between Na2CO3 and sodium borates with thermogravimetry at varying Na/B ratios using the borate compounds Na2B4O7 and
B
NaBO2. They concluded that the decarbonation of Na2CO3 at 925C is complete at Na/B ratios of 2 or lower, in agreement with the studies of Janson. However, Tran et al. [217] found that decarbonation also takes place at Na/B ratios above 2. They proposed that the reaction product is Na3BO3, sodium orthoborate, rather than Na4B2O5, as proposed by
B
Janson. Tran et al. [217] also found that the reaction products can be recarbonated if the surrounding gas is changed from N2 to CO2.
74

The main reactions for the partial autocausticizing concept proposed by Tran et al. [217] are the following: Decarbonation of smelt: NaBO2(s,l) + Na2CO3(s,l) Na3BO3(s,l) + CO2(g) Dissolving of smelt/formation of pulping agents: Na3BO3(s,l) + H2O(l) 2 NaOH(aq) + NaBO2(aq). [Eq. 4.11] [Eq. 4.10]
The implication is that one mole of boron in the liquor cycle can produce two moles of NaOH, instead one mole of NaOH as found by Janson. If the causticizing reactions proceed to completion, the amount of borates in the liquor cycle would be lower to produce white liquor with a specific alkalinity. However, in subsequent studies by Tran et al. [218] and Lindberg et al. [219, 220], it was shown that the decarbonation reaction originally proposed by Tran et al. [217] does not go to completion at Na/B ratios of 3 or higher. Previous studies, unrelated to the autocausticizing process, support these findings. At Na/B ratios above 3 the borate composition is a mixture of Na4B2O5 and Na3BO3. The
B
experimental results of Tran et al. [217] are probably due to the volatilization of Na2CO3, which was not fully accounted for. The properties of carbonate-borate melts in borate autocausticizing will be discussed in more detail in Section 4.4. Mill trials using partial borate autocausticizing have been carried out in North America [221, 222] and in Sweden [223], showing that the concept is a viable means for reducing the lime requirements of pulp mills without substantially affecting mill operations, pulp properties, or quality. A decrease in the dust load was observed in the Swedish trials [223], probably due to the decrease in Na volatilization associated with decomposition of Na2CO3. Fouling patterns of the recovery boilers also changed after the introduction of borates to the liquor cycle, which was expected from the predictions of Hupa et al. [224]. These changes could be managed by the boiler operators, and no signs of increased corrosion were observed.
75
Chapter 4-Borate autocausticizing 4.3 Objective of the experimental study of borate autocausticizing
The objective of this study of borate autocausticizing was to investigate the decarbonation reactions of alkali carbonate and alkali borates involved in reactions occurring in the kraft recovery boiler smelt bed. The emphasis was on the effect of various chemical components and physical conditions in the kraft recovery boiler. The effects of temperature, gas composition, boron content, and alkali metal contents were investigated, along with the reversibility of the autocausticizing reactions. The study was performed using differential thermal analysis and thermogravimetry.
4.4 Properties of borate compounds and phases involved in borate autocausticizing

The element boron is a metalloid and exists at low concentrations in the earths crust (about 15 ppm) [225]. In nature boron occurs exclusively in the form of borates or borosilicates. The most common boron mineral is tourmaline, a highly complex borosilicate which is used mainly as a gemstone or for piezoelectric purposes. The mineral borax, Na2B4O5(OH)48H2O (=Na2B4O710H2O), has been known and used since
B B
ancient times. Also known as tincal, it and the partially dehydrated variant kernite, Na2B4O74H2O, are the most important sources of boron. The term borax is sometimes
B
used for all compounds with the general formula Na2B4O7nH2O (n0). Today, the main
B
use of borates is in the manufacture of fiber glass and heat resistant glass. Boron compounds are also used as bleaching agents (sodium perborate, NaBO3) and reducing agents in organic synthesis (sodium borohydride, NaBH4).
4.4.1 Borates in the recovery boiler
In the borate autocausticizing concept the borate compounds are expected to be sodium borates with an Na/B ratio higher than 1. Na2B4O75H2O is used as the make-up
B
chemical, but after exiting the recovery boiler, the sodium borates will be NaBO2, 76

Na4B2O5 or Na3BO3. Corresponding potassium borates may also form, as potassium is an
B
important nonprocess element in many pulp mills. Alkali borates are soluble in water, and outside the recovery boiler, borates exist mainly in aqueous form in the pulp mill. Ingri [226] reviewed the equilibria between aqueous borate anions. The behavior of borates in aqueous solutions is highly complex due to the formation of various polyanions, which contain several boron atoms per anion, and due to the formation of various hydroxyl-complexes. According to Ingri [226] the borate exists exclusively as a B(OH)4- ion at pH above 11. As most aqueous solutions in the kraft pulping process are strongly alkaline, B(OH)4- should be the main borate species in the aqueous phase in the liquor cycle. The smelt dissolving reactions reported by Janson and Tran should be slightly modified and rather be written as follows:
Na4B2O5(s,l) + 5 H2O(l) 4 Na+(aq) + 2 OH-(aq) + 2 B(OH)4-(aq)

B
[Eq. 4.12] [Eq. 4.13]
Na3BO3(s,l) + 3 H2O(l) 3 Na+(aq) + 2 OH-(aq) + B(OH)4-(aq)
The aqueous chemistry of borates will not be discussed further, as it does not lie within the scope of this study. The behavior of borates under anhydrous conditions is also complex, and it is mainly because borates tend to form polymeric units much as silicates do. A complicating factor is that borates can have both three- and fourfold coordination in the solid and liquid state, forming both trigonal [BO3] and tetrahedral [BO4] polymeric borate units. In contrast, silicates form only tetrahedral units at normal pressure. In borate autocausticizing, the borate compounds of interest are those with an Na/B ratio of 1 or greater. According to the phase diagram of Na2O-B2O3 measured by Milman and Bouaziz [227], the solid sodium borate phases with Na/B equal to or larger than 1 are NaBO2 (=Na2OB2O3);
B
Na6B4O9
B
(=3Na2O2B2O3);
B
Na4B2O5
B
(=2Na2OB2O3);
B
Na10B4O11
B
(=5Na2O2B2O3); and Na3BO3 (=3Na2OB2O3). The authors were unable to identify the composition of the compounds Na6B4O9 and Na10B4O11 with certainty; they may
B B
correspond to the compounds Na5B3O7 (=5Na2O3B2O3) and Na7B3O8 (=7Na2O3B2O3).

B B
Only NaBO2, Na4B2O5, and Na3BO3 were shown to co-exist with a liquid phase.
B
77

Abdullaev et al. [228, 229] also identified the compound Na5BO4 (=5Na2OB2O3).
B
Among the above-mentioned compounds, only NaBO2, Na4B2O5, and Na3BO3 have been
B
observed independently by several researchers. The compounds Na6B4O9, Na10B4O11, and

B B
Na5BO4 are probably of subordinate importance in borate autocausticizing. Na6B4O9 and

B
Na10B4O11 decompose at subsolidus temperatures and will probably not form at the high
B
temperatures in the recovery boiler. Na5BO4 would most likely be carbonated and form Na2CO3 and other sodium borates under recovery boiler conditions. The properties of solid NaBO2, Na4B2O5, Na3BO3, and the corresponding potassium borates will be
B
discussed in Sections 4.4.1.1-4.4.1.3.
4.4.1.1 Alkali orthoborates Alkali orthoborates are compounds containing the simplest borate unit, the trigonal BO33ion. The phases Na3BO3 [227, 230] and KNa2BO3 [231] are known to exist, but no report of potassium orthoborate, K3BO3, has been found. Na3BO3 melts at 675C [227], but the thermal stability of KNa2BO3 is not known. During the synthesis of KNa2BO3 [231], the maximum temperature was 470C. Both Na3BO3 and KNa2BO3 are strongly hygroscopic. The orthoborate ion BO33- is a planar, trigonal unit, which is the building block of the dimeric diborate and trimeric metaborate ions.
4.4.1.2 Alkali diborates
The existence of sodium diborate, Na4B2O5 (also called sodium pyroborate), has been
B
shown [227, 232], but the existence of the corresponding potassium diborate has not been reported. Sodium diborate has a monoclinic crystal structure [232] and melts at 640C [227]. It is also very hygroscopic [232]. The diborate ion B2O54- is a dimer of the trigonal BO33- ion, in which one oxygen atom bridges the boron atoms.
78

4.4.1.3 Alkali metaborates
Alkali metaborates have the general formula MBO2 (M=alkali metal). Potassium is the only alkali metal besides sodium that exists in appreciable amounts in the kraft pulping process. Like several other alkali borates, both NaBO2 and KBO2 are highly hygroscopic and can form several hydrates. Toledano [233] reported that hydrated potassium borates are not stable above 400C. Hydrated sodium borates are not expected to be stable at temperatures above 400C. TGA experiments performed in this study confirm that both NaBO2 and KBO2 are fully dehydrated at 400C. Both NaBO2 and KBO2 are highmelting compounds. The NIST-JANAF thermochemical data compilations give the melting temperature for NaBO2 as 9672C and for KBO2 as 9473C. No intermediate stoichiometric Na-K metaborate phase has been reported, but a solid solution of NaBO2 and KBO2 has been reported [234]. The metaborate ion does not exist as BO2- ions in solid phases, but rather as polymeric ions with the general formula (BO2-)n. The metaborate ion in solid NaBO2 and KBO2 is actually a ring-shaped B3O63- ion [235-237], where, as in LiBO2, it forms endless chains of (BO2-)n [237].
4.4.1.4 Molten alkali borates
Studies of the properties of liquid alkali borates have been conducted mainly in the field of glass science. Borates tend to form polymeric units in the liquid state, which means that they are glass-forming. In the borate autocausticizing concept, molten borates exist only in the recovery boiler, and the overall alkali-to-boron ratio in the smelt or the black liquor will always be higher than 1 in the kraft pulping process. This section discusses the properties of molten alkali borates with an alkali-to-boron ratio higher than 1 and the interaction of the borates with other common species in the recovery boiler smelt, mainly alkali carbonates. The interaction between alkali borates and alkali carbonates in the liquid phase is the interaction of greatest interest in the autocausticizing concept. The carbonate ion
79

depolymerizes the polymeric borate ions, forming smaller borate ions with more nonbridging oxygen atoms and gaseous CO2. The alkali-to-boron ratio will increase for the resulting sodium borate units, which can be seen in the following general reaction:
NaxByO1/2x+3/2y(l) + Na2CO3(l)Na2+xByO1/2x+3/2y+1(l) + CO2(g).

B B
[Eq. 4.14]
Kamitsos et al. [238, 239] studied the speciation of borates in sodium borate-carbonate melts and glasses with Raman and IR spectroscopy. They showed that complex borate units and the metaborate ion, which is a ring unit with the stoichiometry B3O63-, are depolymerized to B2O54- and BO33- as they react with carbonate. B2O54- will further depolymerize to BO33- as more carbonate is added and the temperature is raised. The decarbonation reactions vary with the temperature, the composition of the surrounding gas atmosphere, and the boron concentration in the smelt [220]. Figure 4.3 shows the borate composition calculated as n(Na3BO3)/(n(Na3BO3)+n(NaBO2)) in sodium carbonate/borate mixtures at different B/Na-ratios. The experiments were performed at temperatures between 875C and 1200C in air or N2 [211, 217, 220, 240242] and in CO2 [220, 243-245]. In air and N2, the borate composition varies from NaBO2 at B/Na=1 to a borate composition close to Na3BO3 as B/Na approaches zero. If the autocausticizing reaction according to the concept of Tran et al. [217] (Eq. 4.10) goes to completion, the Na3BO3-composition will be reached when B/Na0.333. The theoretical borate composition if the autocausticizing reaction goes to completion is plotted with solid lines in Figure 4.3. The results from the experiments in air or N2 show that the autocausticizing reaction goes to completion when B/Na>0.5, but when B/Na<0.5 the reaction does not go to completion. In CO2 the borate composition varies between NaBO2 when B/Na=1 and Na4B2O5 at B/Na0, and the autocausticizing reaction is incomplete
B
when B/Na<1. This shows that the extent of the autocausticizing reaction is largely dependent on the composition of the gas atmosphere and the concentration of boron in the carbonate/borate mixture. A low B/Na ratio in the salt mixture and a low partial pressure of CO2 favor the formation of Na3BO3 over NaBO2 in the melt. Carrire et al. [242] and Kamitsos et al. [238, 239] showed that higher temperatures lead to more
80

decarbonation and higher concentration of Na3BO3 in sodium carbonate/borate melts. Tran et al. [217, 218] confirmed these results in later studies.
100 Na3BO3/(Na3BO3+NaBO2) [Mol-%] 80 60
Na4B2O5
Ref [210]: 875 C Ref [216]: 925 C Ref [218]: 900 C Ref [219]: 950 C Ref [239]: 1000 C Ref [240]: 915-1050 C Ref [241]: 950 C Na2CO3+NaBO2 Na Na Na3BO3+CO2 2CO3+NaBO2 3BO3+CO2
Na3BO3
100 Na3BO3/(Na3BO3+NaBO2) [Mol-%] 80 60
Ref [218]: 900 C Ref [219]: 1000 C Ref [242]: 1000 C Ref [243]: 1000 C Ref [244]: 1200 C Na2CO3+NaBO2 Na3BO3+CO2 Na2CO3+NaBO2 Na3BO3+CO2
Na3BO3
Na4B2O5
40 20 0 0.0 0.2 0.4 B/Na 0.6 0.8 1.0
40 20 0 0.0 0.2 0.4 B/Na 0.6 0.8
NaBO2
NaBO2
1.0
Figure 4.3a
Figure 4.3b
Figure 4.3. The borate composition (Na3BO3/(Na3BO3+NaBO2)) of sodium carbonateborate melts as a function of the B/Na ratio on a molar basis in N2 and air (a) or in CO2 (b) at temperatures between 875C and 1200C from different sources [211, 217, 219, 220, 240-245]. References [219, 220] are Publications I and II from this study. The solid line shows the borate composition if the autocausticizing reaction according to Eq. 4.10 goes to completion. The composition of the stoichiometric borate compounds NaBO2, Na4B2O5, and Na3BO3 are plotted for comparison. The borate composition is based on chemical analysis or thermogravimetric measurements of the samples.
B
In a recovery boiler, components such as Cl, K and S play a large role in the behavior of the smelt. Chlorine and sulfur have been considered to play a minor role in the autocausticizing of the smelt [217, 218]. Tran et al. [218] did not observe any effect of NaCl or KCl on the autocausticizing reaction rate, but they observed a lowering of the initial reaction temperature with the addition of KCl. Flood et al. [243] showed that the addition of Na2SO4 does not affect the decarbonation reactions in pure sodium systems. Potassium may play a more significant and direct role in the autocausticizing of the smelt, where potassium borates may react differently than the sodium borates in the autocausticizing of the recovery boiler smelt. Flood et al. [243], Shibata et al. [246], Lim et al. [247], and Karki et al. [248] showed that the decarbonation of alkali carbonates by the addition of borates is lower for potassium systems than for sodium systems, while lithium systems show higher decarbonation than either sodium or potassium systems.
81
4.5 Experimental setup

The reactions of alkali carbonate with alkali metaborate were studied using simultaneous DTA/TGA. Weight changes of the sample and changes in the temperature differences between the samples and a reference were measured. The weight changes correspond to the release or uptake of gas components in the samples, and the changes in the temperature difference are related to endothermic or exothermic reactions in the sample, such as melting, decomposition, and absorption. The experimental parameters were the (Na+K)/B ratio, the K/(Na+K) ratio, the heating rate, the maximum temperature, the time spent at isothermal conditions at maximum temperature, and the CO2/N2 ratio in the gas phase. The starting material was analytical grade alkali carbonates (Na2CO3 and K2CO3) and hydrated alkali metaborates. The experiments were performed using the hydrated alkali metaborates directly (NaBO22H2O) or using dehydrated alkali metaborates (NaBO2 and KBO2). Dehydrated NaBO2 and KBO2 were produced by heating NaBO24H2O and KBO22H2O in a furnace to 400C or 500C, and keeping the samples at isothermal conditions for 30 to 60 min. The mass loss corresponded well to the amount of water in the samples, as reported by the manufacturers. Exposure of the alkali metaborates to air was minimized due to the hygroscopic nature of alkali borates. The sample size was between 5 and 20 mg, and the samples were placed in open platinum cups. The melting temperatures of the pure Na2CO3 and K2CO3 in N2 and CO2, and dehydrated NaBO2 and KBO2 in N2 were also measured. The melting temperatures corresponded well to the literature values. The alkali carbonates melted at slightly higher temperatures in CO2 than in N2. Table 4.1 gives the measured melting temperatures of the compounds. Both a Mettler/Toledo and a TA Instruments Q600 simultaneous DTA/TGA were used in the experiments. The DTA/TGA equipment was calibrated prior to the experiments by standard methods, using materials provided by the manufacturers. The experiments were run using various gas mixtures in order to investigate the interaction of the condensed phases with the gas phase. A gas mixer with electronic flow meters was
82

used to provide the appropriate gas flows and mixtures. The gas flow was between 100 and 200 ml/min. Table 4.1. Melting temperatures of compounds used in the experiments. Compound Na2CO3 K2CO3 NaBO2 KBO2 Tmelt, literature / (C) 858 901 967 947 Tmelt, measured / (C) 100% N2 853 896 968 950 Tmelt, measured / (C) 100% CO2 859 904 -
Experiments with NaBO22H2O as the borate source were all performed using the TA Instruments apparatus. In these experiments no potassium compounds were added. After the samples attained the maximum temperature and were maintained at isothermal conditions, they were cooled to 200C and subsequently reheated to the maximum temperature. The experimental matrix for the experiments with hydrated metaborate is given in Table 4.2. Table 4.2. Experimental conditions for experiments using hydrated borates
Heating Na/B mol/mol 3 3 3 3.2 5 Gas mixture Vol-% 100% N2 15% CO2 + 85% N2 100% CO2 15% CO2 + 85% N2 15% CO2 + 85% N3 rate C/min 20 10 10 20 20 Maximum temperature C 950 1000 1000 950 950 Time min 60 30 30 60 60 at maximum temperature
The experiments using dehydrated alkali metaborates as the borate source were all performed using the Mettler Toledo apparatus. The samples were heated to 900C, kept at isothermal conditions for 60 min, cooled down to 500C, and then reheated to 900C.
83

The heating and cooling rate was 10C/min. The compositional matrix for experiments using dehydrated alkali metaborates is shown in Table 4.3. Table 4.3. Compositional matrix for the experiments using dehydrated alkali metaborates. The (Na+K)/B and K/(Na+K) ratios are calculated on a molar basis. (Na+K)/B K/(Na+K) Vol.-% CO2 in gas 3, 5 0, 0.1, 0.2, 0.5, 1 (0.8*) 0, 1, 100
*The experiment with K/(Na+K)=0.8 was performed only with (Na+K)/B=3 and 100% CO2.
4.6 Results
The starting temperature for the decarbonation of the salt mixtures varies between 650C and 820C with a minimum at K/(K+Na)=0.5. The initial reaction temperature as a function of K/(K+Na) is shown in Figure 4.4. It is likely that the sample begins to melt simultaneously with the start of the decarbonation reaction. Visual observation of the samples after the experiments suggests that the samples were molten at some stage. No other thermal events which would indicate a separate melting of the sample were observed. In the pure sodium mixtures, the initial reaction temperature is strongly influenced by the composition of the gas atmosphere. In N2, the reaction begins at around 700C, and in CO2, the reaction begins at around 800C. With 1% CO2 the reaction starts at around 740C. The Na/B ratio does not affect the reaction temperatures. In experiments with higher fractions of potassium, K/(K+Na), the effect of the gas composition is similar but less pronounced. In pure potassium systems, the reaction starts at around 800C.
84
850
100 % N2, (Na+K)/B=3 1 % CO2, (Na+K)/B=3 100 % CO2, (Na+K)/B=3 100 % N2 (Na+K)/B=5 1 % CO2, (Na+K)/B=5 100 % CO2, (Na+K)/B=5
800
750 T [C] 700 650 600 0 0.2 0.4 0.6 0.8 1 n(K)/(n(K)+n(Na))
Figure 4.4. Starting temperature for the autocausticizing reaction of alkali metaborate/carbonate mixtures as a function of n(K)/(n(K)+n(Na)). The experiments were performed in different gas atmospheres, with varying alkali-to-boron ratios. The sample weight decreases after the initial reaction temperature is attained. Weight loss in the samples is attributed to the release of CO2 from the carbonate in the melt. As the maximum temperature of 900C is reached, the weight loss continues in N2, but in pure sodium mixtures the weight loss stops at 900C, when the gases contain 1 % or 100 % CO2 (Figure 4.5). This suggests that equilibrium is attained when the temperature had reaches 900C if the surrounding gas atmosphere containes CO2. In N2, the decarbonation reaction may continue, but volatilization of sodium or boron components might also contribute to the weight loss. The pure salts Na2CO3, K2CO3, NaBO2, and KBO2 all tend to volatilize markedly at temperatures above their melting points. The carbonates volatilize to a much larger extent in atmospheres of pure N2 than
85

in atmospheres of CO2 [249]. The salt KBO2 starts to volatilize below its melting point (950C) at around 900C, and K2CO3 has been shown to volatilize below its melting point (901C) [249]. The reaction mechanisms of the volatilization of the pure salts are however not fully understood.
100 95 90
100 % CO2
1000 900 800 700
Weight-%
500 80 75 70 65 0 20 40 60 80 100 120 140 160 180 200 220 Time [min]
Na/B=5 100 % N2 Na/B=3
400 300 200 100 0
Figure 4.5. Weight curves of samples from TGA experiments with Na2CO3/NaBO2 mixtures (Na/B=3: black; Na/B=5: gray) in different gas atmospheres (100% CO2; 1% CO2/99% N2; 100% CO2) as function of time. The temperature profile (dashed line) of the experiments is plotted relative to the right y-axis. As the temperature is lowered to 500C, the weight increases in the experiments run in CO2, which clearly shows that the salts are recarbonated as temperatures are lowered. Both in 1% CO2 and in 100% CO2, the recarbonation is close to complete in sodium systems (97-99% of the original weight), which suggests that only CO2 is released from the sodium salt mixtures if the surrounding CO2 atmosphere is controlled. 86
T [C]
85
1 % CO2
600

The fact that recarbonation is not fully complete is probably due to kinetic or diffusion related constraints of the recarbonation reaction at the lower temperatures. As almost no weight loss occurs under the isothermal conditions at 900C in the experiments with controlled CO2 atmospheres, the release of gaseous sodium or boron components seems subordinate to the release of CO2. As the temperature is raised again, decarbonation recurs at the same temperature as in the first heating. The thermogravimetric curves for pure sodium systems are shown in Figure 4.5. In pure potassium mixtures the decarbonation reaction starts at around 800C (Figure 4.6). Some weight loss occurs at temperatures below 900C. Under isothermal conditions at 900C, the potassium mixtures decrease considerably in weight. This is considered to be due mainly to the volatilization of KBO2 and/or K2CO3, based on the fact that the pure salts already show tendencies to volatilize at 900C. Flood et al. [243] showed that the borate composition is close to KBO2 in potassium carbonate borate melts, independent of the B/K-ratio at B/K<1 at 1000C in 1 atm CO2. Lim et al. [247] measured carbonate retention in potassium borate glasses made from K2CO3 and B2O3 at 1000C. The potassium that is not bound as carbonate at B/K ratios between 0.2 and 1 has a composition that varies between K2B4O7 and KBO2, which shows that K2CO3 and
B
KBO2 have not reacted according to Equation 4.15 to any great extent in the experiments by Flood et al. [243] and Lim et al. [247]. Almost no recarbonation occurs in pure potassium systems, which indicates that the influence of decarbonation analogous to Equation 4.15 is subordinate to the volatilization of K2CO3 or KBO2 for the weight loss at 900C in potassium systems. The decarbonation reaction of potassium compounds is expressed as K2CO3 (s,l) + KBO2 (s,l) K3BO3 (s,l) + CO2 (g). [Eq. 4.15]
The thermogravimetric curves for pure potassium systems are shown in Figure 4.6.
87

100 95
100 % CO2
1000 900 800 700 600 500

1 % CO2
90
Weight-%
80 75 70 65 0
400 300
100 % N2
200 100 0
20 40 60 80 100 120 140 160 180 200 220
Time [min]
Figure 4.6. Weight curves of samples from TGA experiments with K2CO3/KBO2 mixtures in different gas atmospheres (100% CO2, 1% CO2/99% N2, 100% CO2) as function of time. The temperature profile (dashed line) of the experiments is plotted relative to the right y-axis. The extent of decarbonation was calculated based on the mass loss, assuming that it occurred exclusively in the form of gaseous CO2. To compare the different experiments, the start of the isothermal conditions at the maximum temperature maximum was chosen as the time to calculate the extent of the autocausticizing reaction. In the experiments with pure sodium mixtures and controlled CO2 in the gas phase, the mass loss was negligible during the isothermal conditions, suggesting that equilibrium had been attained. This was not the case for the experiments performed in N2 or for systems containing potassium, probably due to the release of gas components other than CO2. However, quantification of the release of other gas components was not possible in this study. The borate composition was calculated as the molar ratio of alkali orthoborate to
88
T [C]
85

alkali orthoborate and alkali metaborate. In theory, this ratio can be lower than zero or higher than 1, but this did not occur in these experiments. This ratio is convenient as it also directly describes the conversion of the alkali metaborates into orthoborates according to the autocausticizing reaction given by Equation 4.10. As K/(K+Na) increases, the extent of the autocausticizing reaction decreases. In pure potassium systems, autocausticizing is almost nonexistent in 100% CO2. For all compositions, autocausticizing decreases as the concentration of CO2 in the controlled gas atmosphere increases.
1
100% N2, (Na+K)/B=3 1% CO2, (Na+K)/B=3 100% CO2, (Na+K)/B=3 100% N2, (Na+K)/B=5 1% CO2, (Na+K)/B=5 100% CO2, (Na+K)/B=5
0.8 n(M3BO3)/(n(M3BO3)+n(MBO2))
0.6
0.4
0.2
0 0 0.2 0.4 0.6 0.8 1 n(K)/(n(K)+n(Na))
Figure 4.7. The extent of borate conversion at 900C of the autocausticizing reaction according to Eq. 4.10 plotted against the molar potassium-to-alkali ratio at different alkali-to-boron ratios and in different gas atmospheres
89
In samples with (Na+K)/B=5, there is an excess of carbonate based on the stoichiometry of the autocausticizing reaction (Equation 4.10). The experiments show trends similar to those for (Na+K)/B=3, but most of the compositions show higher n(M3BO3)/(n(M3BO3) +n(MBO2)) (M=Na,K) in experiments with (Na+K)/B=5. This can also be expected based on chemical equilibrium considerations. In pure sodium systems, the borate composition is 91 mol-% Na3BO3, 9 mol-% NaBO2 in N2 and 84 mol-% Na3BO3, 16 mol-% NaBO2 in 1% CO2, which shows that it is possible to convert almost all of the borate to Na3BO3 when Na/B>5 (B/Na<0.2) under conditions similar to those occurring in the smelt bed of a recovery boiler. The extent of the borate autocausticizing at 900C as a function of molar ratio of K/(Na+K) is shown in Figure 4.7. Under isothermal conditions at 900C for 60 min, the weight decreases in many of the experiments. The weight loss per time unit is dependent on the K/(K+Na) ratio; high potassium ratios correspond to higher weight loss. For pure sodium systems with 1% or 100% CO2, the weight loss is close to zero at 900C. In pure potassium systems, the measured weight loss in some experiments is higher than the theoretically predicted weight loss under the assumption that CO2 is the only volatilized component. As the samples are cooled from 900C to 500C, recarbonation of the salts can occur if the experiments are run in 1% or 100% CO2. As the n(K)/(n(Na)+n(K)) is lowered, recarbonation decreases, and no recarbonation occurs in pure potassium systems. This also indicates that in potassium-rich systems, a volatilization of alkali or boron components occurs instead, while in sodium-rich systems, CO2 is released and the alkali and boron components are less volatile.
4.7 Discussion
The decarbonation of alkali carbonate/borate mixtures is dependent on several chemical and physical factors. An increase in potassium in the smelt leads to lower conversion, but it will also lead to lower initial reaction temperatures, which can have positive effects on borate conversion in the kraft recovery boiler. The molar ratio of potassium-to-alkali in
90

virgin black liquors is generally around 0.05, and slightly higher in black liquors that are fired. These low potassium contents do not affect borate conversion significantly. The CO2 in the surrounding gas phase has a significant effect on borate conversion in the autocausticizing reactions. High CO2 partial pressure inhibits decarbonation of the alkali carbonates. In the char bed of a kraft recovery boiler, the CO2 partial pressure will be low due to the presence of char carbon. This could enhance the autocausticizing reactions. Similarly, autocausticizing in burning black liquor droplets may be enhanced by the presence of char carbon. The recarbonation of sodium-rich salt mixtures shows that recovery boiler smelt is highly sensitive to temperature and the CO2 partial pressure in the smelt bed and that autocausticized smelt can be recarbonated in the smelt bed if it is exposed to lower temperatures and higher CO2 pressures. The borate-carbonate ratio in the smelt or black liquor affects the conversion of sodium metaborate into sodium orthoborate. A higher carbonate-to-borate ratio increases the conversion of borates into orthoborate. Components such as sulfate, sulfide, and chloride do not affect the autocausticizing reaction to a great extent. In this study it was shown that borate conversion is high in N2 and in gas containing 1% CO2 when Na/B=5 (85-90% borate conversion). In mill trials using partial borate autocausticizing, the Na/B ratios have been similar to or higher than those considered in this study. The experiments show that the expected degree of autocausticizing can be attained under full-scale conditions. However, the viability of partial autocausticizing at pulp mills is dependent on both economic and operational factors, which are mill-specific. Thermodynamic modeling of the autocausticizing reaction and of the melting properties of borate-containing salt mixtures would yield valuable information about the chemical processes that can occur in kraft recovery boilers firing boron-containing black liquors. Unfortunately, there is a lack of published thermodynamic data for the critical phases, especially Na3BO3 and Na4B2O5. Additionally, the melting properties of alkali
B
salt mixtures containing borates have been poorly studied. Hupa et al. [224] made thermodynamic predictions about the combustion of boron-containing black liquors and about the behavior of the borate-containing alkali salt mixtures involved in partial borate autocausticizing. However, a more in-depth evaluation of the thermodynamic properties
91

of the borates is needed for more accurate predictions. The experimental results in this study can be used as input for a future thermodynamic evaluation of the thermodynamic properties of solid alkali borates and borate-containing salt melts.
4.8 Conclusions
This study shows that the autocausticizing reaction between Na2CO3 and NaBO2 is a reversible reaction which can give high borate conversion under conditions found in the smelt bed in kraft recovery boilers. High concentrations of potassium in the black liquor or smelt and high CO2 partial pressure in the gas phase have negative effects on the autocausticizing reactions, decreasing the conversion of the borates into the orthoborate form. The experimental data obtained in this study can be used to evaluate the thermodynamic properties of sodium borates involved in the borate autocaustcizing concept, making possible accurate thermodynamic predictions of autocausticizing.
92
Chapter 5-Conclusions and implications 5. Conclusions and implications

The thermochemistry and melting properties of alkali salt mixtures involved in black liquor and biomass combustion were studied by evaluating and optimizing the thermodynamic data for all known phases in the Na+,K+/CO32-,SO42-,S2-,S2O72-,Sx2-,Cl-, Va- system using experimental data as input. Additional experimental data for melting temperatures in the ternary NaCl-Na2CO3-Na2SO4 and KCl-K2CO3-K2SO4 systems were obtained by simultaneous differential thermal analysis and thermogravimetry, and the results were used as input for the thermodynamic optimization. The thermodynamic properties of the liquid phase were modeled using the Modified Quasichemical Model in the Quadruplet Approximation, which is a thermodynamic model developed especially for molten salts. The resulting thermodynamic database reproduces the solid-liquid equilibria of the binary, ternary, and quaternary systems to within the experimental uncertainties. The database of thermodynamic data for all phases can be used, along with other databases and Gibbs energy minimization software, to calculate the phase equilibria and all the thermodynamic properties of multicomponent alkaline salt mixtures, which are of great importance for addressing ash-related problems in biomass and for studying processes in black liquor combustion. Phenomena such as deposit formation and buildup on superheater tubes in the recovery boiler are connected to the formation of a liquid phase in alkali salt particles. Also, different types of corrosion are also related to the formation of a molten phase. The melting behavior of alkali salts involved in such processes can be calculated with the obtained thermodynamic database. Predictions of the melting properties are also useful for shedding light on the behavior of the smelt bed in a kraft recovery boiler The behavior of alkali salt mixtures of alkali carbonates and alkali borates was studied using simultaneous differential thermal analysis and thermogravimetry in order to identify the effect of chemical and physical variations on the borate autocausticizing concept. It was shown that the borate autocausticizing reactions are reversible and that high temperatures and low borate contents enhance the conversion of borates into the preferred orthoborate form, while high potassium content and high CO2 partial pressures inhibit the autocausticizing reaction. It was shown that high conversion of the borates can 93
Chapter 5-Conclusions and implications

be attained under conditions prevalent in the char bed of a kraft recovery boiler. The experimental results can be used as input for future thermodynamic evaluations of boratecontaining alkali salt systems involved in the combustion of boron-containing black liquors.
94
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235. 236. 237. 238. 239. 240. 241. 242. 243. 244. ZACHARIASEN, W.H. The crystal structure of potassium metaborate, K3(B3O6). J. Chem. Phys. 1937, 5 919-922. FANG, S.-M. The crystal structure of sodium metaborate, Na3(B3O6). Zeitschrift fuer Kristallographie, Kristallgeometrie, Kristallphysik, Kristallchemie 1938, 99 1-8. LEONYUK, N.I. Structural aspects in crystal growth of anhydrous borates. Journal of Crystal Growth 1997, 174(1-4), 301-307. KAMITSOS, E.I.;KARAKASSIDES, M.A. Structural studies of binary and pseudo binary sodium borate glasses of high sodium content. Phys. Chem. Glasses 1989, 30(1), 19-26. KAMITSOS, E.I.;KARAKASSIDES, M.A.;PATSIS, A.P. Spectroscopic study of carbonate retention in high-basicity borate glasses. J. Non Cryst. Solids 1989, 111(2-3), 252-262. KASPER, J.E.;FELLER, S.;SUMCAD, G.L. New sodium borate glasses. J. Am. Ceram. Soc. 1984, 67(4), C71-C72. RITCHIE, C.F.;BLACK, L.G. Method of producing caustic borate products. US Patent 2146093 1939. CARRIRE, E.;GUITER, H.;THUBERT, F. Action de l'anhydride borique sur le carbonate de sodium. Bull. Soc. Chim. Fr. 1949, 16(5), 796-801. FLOOD, H.;FRLAND, T.;ROALD, B. The acidic and basic properties of oxides. III. Relative acid-base strenghts of some polyacids. Acta Chem. Scandinavica 1947, 1 790-798. IWASE, M.;WATANABE, H.;NAKAYAMA, N.;HORI, H. Solubilities of CO2 in candidate glasses for nuclear waste immobilisation. Part 1. Systems, Cs2O+SiO2, Cs2O+B2O3, Rb2O+SiO2 and Na2O+B2O3. Glass Technol. 1994, 35(1), 41-47. KAWAHARA, T.;YAMAGATA, K.;SANO, N. The CO2 solubilities of high basic melts. Steel Res. 1986, 57(4), 160-165. SHIBATA, M.;SANCHEZ, C.;PATEL, H.;FELLER, S.;STARK, J.;SUMCAD, G.;KASPER, J. The density of lithium borate glasses related to atomic arrangements. J. Non Cryst. Solids 1986, 85(1-2), 29-41. LIM, H.P.;KARKI, A.;FELLER, S.;KASPER, J.E.;SUMCAD, G. The density of potassium borate glasses related to atomic arrangements. J. Non Cryst. Solids 1987, 91(3), 324-332. KARKI, A.;FELLER, S.;LIM, H.P.;STARK, J.;SANCHEZ, C.;SHIBATA, M. The density of sodium-borate glasses related to atomic arrangements. J. Non Cryst. Solids 1987, 92(1), 11-19. LEHMAN, R.L.;GENTRY, J.S.;GLUMAC, N.G. Thermal stability of potassium carbonate near its melting point. Thermochim. Acta 1998, 316(1), 1-9.
245. 246. 247. 248. 249.
109
Appendix A
Thermodynamic properties of pure stoichiometric phases used in the present optimization. Thermodynamic data optimized in this work is indicated by *.
T range /K
o H 298 .15 K
o S 298 .15 K
Cp
(Jmol-1K-1)
Reference
(Jmol-1)
(Jmol-1K-1)
Gas
K(g) 298.15-1900 1900-4300 4300-5600 5600-6000 K2(g) 298.15-1000 1000-4500 Na(g) 298.15-2000 2000-4000 4000-6000 Na2(g) 142070.0 298.15-1700 230.2430 107300.0 153.6670 20.7879 -320.9045+0.0182633(T/K)+174135380(T/K)-2-726550.4(T/K)-1 +27946.6911(T/K)-0.5 580.6437-2393169990(T/K)-2-3929424.2(T/K)-1-87921.1790(T/K)-0.5 166.8484-0.0264705(T/K)-3021766(T/K)-2+60564.8(T/K)-1 -5016.4727(T/K)-0.5 [52] 123683.0 249.6900 212.7096-0.0488067(T/K)-2556985(T/K)-2+64186.8(T/K)-1 -5986.7190(T/K)-0.5 90.4840-0.0024884(T/K)-48024379(T/K)-2+213919.6(T/K)-1 -6883.4754(T/K)-0.5 [52] 89000 160.3400 20.7080+7.677971010-5(T/K)+5916.18(T/K)-2 -648.4359+0.0377245(T/K)+327221723(T/K)-2-1384080(T/K)-1 +53851.3706(T/K)-0.5 972897.1709-98.2407(T/K)+0.0079252(T/K)2-2.84922810-7(T/K)3 +1202498191(T/K)-1-62555672.4686(T/K)-0.5 285.6755+6646736407(T/K)-2-2551763.5(T/K)-1 [52]
[52]
1700-4400 4400-6000 O2(g) 298.15-1000 1000-4000 4000-6000 S(g) 298.15-1000 1000-3400 3400-10000 S2(g) 298.15-1000 1000-3400 3400-6000 S3(g) 298.15-1000 1000-6000 S4(g) 298.15-900 900-6000 S5(g) 298.15-900 900-2800 2800-6000 S6(g) 298.15-1600 1600-4200 4200-6000 S7(g) 298.15-1500 1500-6000 111890.0 404.8460 101315.0 357.8040 132993.0 354.0780 135632.0 293.5570 144738.0 276.2890 128600.0 228.1640 277180.0 167.8270 0 205.147
-7383.7074+0.7085598(T/K)+1886772999(T/K)-2-4.1391510-5(T/K)2 -10772099.0(T/K)-1+495482.0638(T/K)-0.5 -637.0898+1296595123(T/K)-2-4248696.2 (T/K)-1 +105287.7900(T/K)-0.5 26.9241+0.0169787(T/K)+229 329(T/K)-2-6.766165210-6(T/K)2 -79.1617(T/K)-0.5 89.6813-0.0014474(T/K)-18 682 686(T/K)-2+95 804.0(T/K)-1 -4126.5372(T/K)-0.5 249.1731-1 184 978 422(T/K)-2+1674792.0(T/K)-1 -34 935.6696(T/K)-0.5 25.7047-0.0075027(T/K)+3.293310-6(T/K)2-6901(T/K)-2 19.8174+0.0004601(T/K)+7.1210-8(T/K)2+1140873(T/K)-2 24.0593+1.2010-6(T/K)-1.2210-8(T/K)2-18736330(T/K)-2 34.0968+0.0046509(T/K)-1.112910-6(T/K)2-257187(T/K)-2 34.0474+0.0042300(T/K)-5.50010-7(T/K)2-351436.9(T/K)-2 36.1923+0.0011862(T/K)+4.5310-8(T/K)2+14968210(T/K)-2 52.9456+0.0086770(T/K)-4.009810-6(T/K)2-553877(T/K)-2 58.1624+1.45810-5(T/K)-1.4610-9(T/K)2-1117610(T/K)-2 72.6797+0.0180823(T/K)-8.828910-6(T/K)2-1010556(T/K)-2 83.0503+3.65610-5(T/K)-3.7210-9(T/K)2-2047177(T/K)-2 74.9902+0.070672950(T/K)-3.4612410-5(T/K)2-454141(T/K)-2 130.5370-0.0157580(T/K)+2.595710-6(T/K)2-6850514(T/K)-2 103.9801-4.51810-5(T/K)+4.7610-9(T/K)2+15665430(T/K)-2 130.1838+0.0008305(T/K)+2.562810 (T/K) -1558237(T/K) 155.3363-0.0040624(T/K)+1.06610-7(T/K)2-29816560(T/K)-2 147.3935-0.0031858(T/K)+2.007710-7(T/K)2+16093550(T/K)-2 153.2939+0.0062057(T/K)-2.196910-6(T/K)2-1880136(T/K)-2 157.9591+4.882810-6(T/K)-4.410-10(T/K)2-2568259(T/K)-2 [54]
-6 2 -2
[52]
[54]
[54]
[54] [54] [54]
[54]
S8(g) 298.15-800 800-1500 1500-3900 3900-6000 SO2(g) 298.15-1700 1700-6000 SO3(g) 298.15-1000 1700-6000
100215.0c
432.5360
166.1987+0.0219772(T/K)+8.332510-6(T/K)2-1507268(T/K)-2 181.0091+0.0405053(T/K)-1.8272610-5(T/K)2-9571872(T/K)-2 208.7199-0.0122793(T/K)+1.547910-6(T/K)2+5886180(T/K)-2 180.3439+0.0005160(T/K)-3.1010-8(T/K)2+43690900(T/K)-2 53.0280+4.34291810-5(T/K)+2 282 495(T/K)-2-24 439.3(T/K)-1 +744.8739(T/K)-0.5 76.5423-22 531 507(T/K)-2+56 025.9(T/K)-1-1819.1530(T/K)-0.5 91.2686+0.0071051(T/K)+1 916 937(T/K)-2-5.30908210-6(T/K)2 -19 025.3(T/K)-1 82.0191-3 955 058(T/K)-2-7669.6(T/K)-1+175.8783(T/K)-0.5
[54]
-296842 .0
248.212
[52]
-395765.0
256.769
[52]
Liquid
K(l) 298.15-337 337-2200 4500-6000 K2CO3(l) 298.15-800 800-3000 KCl(l) 298.15-3000 K2S(l) K2S2(l) K2S3(l) 298.15-3000 -346484.7 298.15-820 820-3000 -424454.9 298.15-3000 -460585.0 209.5113 175.3419 Cp(K2S(l))+Cp(S(l)) Cp(K2S(l))+ 2Cp(S(l)) 141.1725 66.9194+0.0260108(T/K) 100.9600 * * -421824.9 86.5225 73.5966 [52] -1130390.3 170.6837 266.1904-4284010(T/K)-2 +2.71415510-5(T/K)2 -4146.0845 (T/K)-0.5+27059.9(T/K)-1 209.2000 [53] 2320.0 71.5718 77.0571-0.292422(T/K)-486770(T/K)-2+5.09694810-4(T/K)2 +2.0122110-17(T/K)6 39.2886-0.0243348(T/K)-86502(T/K)-2+1.5863210-5 T2 50.3657-252082087(T/K)-2313129.0(T/K)-1-5746.3839(T/K)-0.5 [55]
[52]
K2S4(l) 298.15-3000 K2S5(l) 298.15-3000 K2S6(l) 298.15-3000 K2S7(l) 298.15-3000 K2S8(l) 298.15-3000 K2SO4(l) 298.15-800 800-3000 K2S2O7(l) Na(l) 298.15-371 371-2300 NaCl(l) 298.15-1500 1500-3000 Na2CO3(l) 298.15-723 723-3000 Na2S(l) 298.15-970 970-3000 Na2S2(l) Na2S3(l) 298.15-3000 Na2S4(l) 298.15-3000 Na2S5(l)
-475795.2 -480545.4 -480065.5 -476970.7 -472568.4 -1393665.4
243.6807 277.8501 312.0196 346.1890 380.3584 211.5102 Cp(K2S(l))+ 3Cp(S(l)) Cp(K2S(l))+ 4Cp(S(l)) Cp(K2S(l))+ 5Cp(S(l)) Cp(K2S(l))+ 6Cp(S(l)) Cp(K2S(l))+ 7Cp(S(l)) -223.9595+0.3505255(T/K)-6 082 803(T/K)-2-7.21025210-5(T/K)2 +5621.6377(T/K)-0.5 201.4600 267.0000
* * * * * [52]
-1971380.1 298.15-3000 2584.85
285.7865 58.2644 51.0394-0.144613(T/K)-264308(T/K)-2+2.61829710-4(T/K)2 +1.122823810-16(T/K)6 38.1199-0.0194917(T/K)-68684(T/K)-2+1.02398410-5 (T/K)2 77.7638-0.0075312(T/K) 66.9440
* [56] [55]
-394956.0 -1356407.9 -328289.3 -374879.5 298.15-3000 -396365.7 -405299.8 -407958.0
76.0761 181.1470 131.7243 163.3834 195.0424 226.7014 258.3604 Cp(Na2S(l))+Cp(S(l)) Cp(Na2S(l))+ 2Cp(S(l)) Cp(Na2S(l))+ 3Cp(S(l))
[54] [52] * [52] * * * *
87.1219+0.0262992(T/K)+110905(T/K)-2+1.66682310-4(T/K)2 197.0330 77.4634+0.0175631(T/K) +27880(T/K)-2-2.290310-6(T/K)2 92.0480
298.15-3000 Na2S6(l) 298.15-3000 Na2S7(l) 298.15-3000 Na2S8(l) 298.15-3000 Na2SO4(l) -1356407.9 298.15-800 800-3000 Na2S2O7(l) S(l) 298.15-388 388-428 428-432 432-453 453-717 717-1300 -1895345.3 298.15-3000 1525.8 35.8430 283.6012 181.1470 -402596.0 353.3375 -405429.3 321.6785 -407478.1 290.0195
Cp(Na2S(l))+ 4Cp(S(l)) Cp(Na2S(l))+ 5Cp(S(l)) Cp(Na2S(l))+ 6Cp(S(l)) Cp(Na2S(l))+ 7Cp(S(l)) 191.8357+0.0598038(T/K)-3 775 793(T/K)-2+52 366.0(T/K)-1 -3163.706(T/K)-0.5 197.0330 244.8000 15.5040+0.0372580(T/K)+1.496510-6(T/K)2+227890(T/K)-2 19762.4000-65.5855000(T/K)+0.0613285000(T/K)2-529347000(T/K)-2 57607.3000-270.6090000(T/K)+0.3179840000(T/K)2 1371.8500-5.6900700(T/K)+0.0060828000(T/K)2 -202.9580+0.5063830(T/K)-3.11300110-4(T/K)2+16404400(T/K)-2 32.0000
* * * [52]
* [57] [55]
Solid
K(s) 298.15-337 337-2200 K2CO3(s, ) 298.15-1178 1178-3000 K2CO3(s, ) 298.15-1178 1178-3000 -114952.0 155.8499 -1150182.0 155.5190 266.1904-4284010(T/K) +2.71415510 (T/K) -4146.0845 (T/K)-0.5+27059.9(T/K)-1 209.2000
-2 -5 2
64.6800
77.0571-0.292422(T/K)-486770(T/K)-2+5.09694810-4 (T/K)2 39.2886-0.0243348(T/K)-86502(T/K)-2+1.5863210-5 (T/K)2 -5.531761023(T/K)-10
[55]
[52]
266.1904-4284010(T/K)-2 +2.71415510-5(T/K)2 -4146.0845 (T/K)-0.5+27059.9(T/K)-1 209.2000
[52]
KCl(s) 298.15-2500 2500-3000 KNa2(s) KNaS2O7(s) 298.15-692 K2S(s) 298.15-800 800-1050 1050-1100 1100-1400 1400-1401
-436684.1
82.5503 40.0158+0.025468(T/K)+364845(T/K) 103.7442

-2
[53]
-1033.2 -1974414.5 -376560.0
166.9416 239.1637 115.0600 2Cp(Na(s))+Cp(K(s)) 0.5Cp(Na2S2O7(s)) +0.5Cp(K2S2O7(s, )) 66.9153+0.0260208(T/K) -1781.8925+1.5214365(T/K)+417584199(T/K)-2 -4924.9043+2.8110052(T/K)+2389917691(T/K)-2 142.3400 100.9600
* * [52]
K2S2(s) 298.15-750 K2S3(s) 298.15-410 410-562 K2S4(s) K2S5(s) K2S6(s) K2SO4(s, ) 298.15-1342 1342-3000 K2SO4(s, ) K2S2O7(s, ) K2S2O7(s, ) Na(s)
-447500.0 -471100.0 -480200.0 298.15-432 -497900.0 298.15-480 -496700.0 298.15-470 -1437706.0
146.0000 192.0000 238.0000
79.9981+ 0.1017130(T/K)-6.3165810-5(T/K)2 464.2148-1.9882368(T/K) +2.928381610-3(T/K)2 1043.4478-4.4810640(T/K)+0.0056233(T/K)2 43.0000+0.2900000(T/K)
* [58] * [58] * [58] * [58] * [58] [52]
249.0000 286.4000 175.5440
514.2554-2.4777648(T/K) +0.0044019864(T/K)2 899.9784-3.9555536(T/K) +0.0056421240(T/K)2 -223.9595+0.3505255(T/K)-6 082 803(T/K)-2-7.21025210-5(T/K)2 +5621.6377(T/K)-0.5 201.4600 114.3634+0.081251(T/K) 201.46
-1424200.5 298.15-1342 1342-3000 -1997959.4 298.15-591 -1989823.1 298.15-692 0
192.4077 258.0887 134.6525+0.1770000(T/K) 261.0446 260.0000 51.3000
[52] * [56] * [56] [55]
298.15-371 371-2300 Na2CO3(s, ) 298.15-758 758-1131 1131-3000 Na2CO3(s, ) 298.15-758 758-1131 1131-3000 Na2CO3(s, ) 298.15-758 758-1131 1131-3000 NaCl(s) 298.15-2000 2000-3000 Na2S(s) -370284.0 298.15-1000 1000-1276 1276-1445 1445-1700 1700-1701 -403421.7 298.15-1000 -425094.4 298.15-1000 -424257.6 298.15-515 -1380899.0 298.15-1157 1157-3000 Na2SO4(s, IV) -1387559.0 298.15-1157 1157-3000 150.1570 160.1320 241.4168 202.9240 131.7960 100.4160 -411119.8 72.1322 -1127864.0 142.7249 -1130400.0 139.3793 -1130768.0 138.7970
51.0394-0.1446133(T/K)-264308(T/K)-2+2.61829710-4 (T/K)2 38.1199-0.0194917(T/K)-68684(T/K)-2+1.02398410-5 (T/K)2 -1.4464171025(T/K)-10 87.1219+0.0262992(T/K)+110905(T/K) +1.66682310 (T/K) 117.3602+0.10574432(T/K)+20126029(T/K)-2-64039.3(T/K)-1 189.5350
-2 -4 2
[52]
87.1219+0.0262992(T/K)+110905(T/K)-2+1.66682310-4(T/K)2 117.3602+0.10574432(T/K)+20126029(T/K)-2-64039.3(T/K)-1 189.5350 87.1219+0.0262992(T/K)+110905(T/K)-2+1.66682310-4(T/K)2 117.3602+0.10574432(T/K)+20126029(T/K)-2-64039.3(T/K)-1 189.5350 45.9403+0.016318(T/K) 78.5755 78.9784+0.0138953(T/K) -29076(T/K)-2 -2151.5344+1.4883211(T/K)+417584199(T/K)-2 -5403.9151+2.5759776(T/K)+3791261493(T/K)-2 133.8880 92.0480 82.0080+0.0557288(T/K) 149.7872 179.0752 191.8357+0.0598038(T/K)-3 775 793(T/K)-2+52 366.0(T/K)-1 -3163.7059(T/K)-0.5 197.0330 127.6519+0.0961269(T/K)+3401(T/K)-2-8409.9(T/K)-1 197.0330
[52]
[52]
[53] * [52]
Na2S2(s,) Na2S4(s) Na2S5(s) Na2SO4(s, I)
* [52] * [59] * [60] [52]
[52]
Na2SO4(s, V) Na2S2O7(s)
-1387816.0 298.15-1157 1157-3000 -1949561.3 298.15-590 590-633 633-673 673-675 0 298.15-368 368-1300
149.5950 217.2828
127.6519+0.0961269(T/K)+3401(T/K)-2-8409.9(T/K)-1 197.0330 110.2000+0.1870000(T/K) -1547.9000+2.9911000(T/K) 485 376.0-1524.6(T/K)+1.1982(T/K)2 110.2000+0.1870000(T/K)
[52] * [57] * * [55]
S(s, ,ortho) S(s, ,mono) 298.15-388 388-1300

a
32.0700
11.0070+0.0530580(T/K)-4.6526010-5(T/K)2 17.9418+0.0217903(T/K)-8.415310-6(T/K)2-79820(T/K)-2 17.3180+0.0202430(T/K) 21.1094+0.0172083(T/K)-6.708410-6(T/K)2-241480(T/K)-2
361.6
33.0397
[55]
Enthalpy relative to the enthalpy of the elements in their stable standard states at 298.15 K. Absolute (third law) entropy. c o of S8(g) is changed from the SGTE-value [54] of 101277 J/mol to 100215 J/mol to get better agreement with the boiling H 298 .15 K temperature of sulfur (Peter Waldner, private communication 2004).
b
Appendix B
Thermodynamic functions for the solid solutions. G for the stoichiometric compounds is derived from appendix A.
Na-K alloy solid solution, BCC structure:
One sublattice, one site:
K, Na
o 1 o 1 1 e G m /( J mol 1 ) = y Na GNa ( s ) /( J mol ) + y K G K ( s ) /( J mol ) + RT ( y Na ln y Na + y K ln y K ) + Gm /( J mol ) e 1 Gm /( J mol 1 ) = y Na y K ( L0 Na , K + LNa , K ( y Na y K ))
L0 Na , K = 8305.24 L1Na ,K = 706.47 + 4.184(T / K )

Alkali chloride solid solution, NaCl-KCl:
Two sublattices:
Cationic sublattice, C, one site: Anionic sublattice, A, one site:
K+, Na+ Cl-
1 C A C A C C C C e o o /( J mol 1 ) + y K /( J mol 1 ) + RT ( y Na ) G m /( J mol 1 ) = y Na + yK + y G + y G + + ln y + ln y + ) + Gm /( J mol Cl Na + :Cl Cl K :Cl Na + K 1 1 o o ) = GNaCl GNa + 2 /( J mol ( s ) /( J mol ) :S 1 1 o o ) = GKCl GK + 2 /( J mol ( s ) /( J mol ) :S
0 e C C A C C /( J mol 1 ) = y Na Gm + L1Na + ,K + :Cl ( y Na + y + y (L + y + )) K Cl Na + , K + :Cl K
L0 = 15972 + 32.796(T / K ) 5.593(T / K ) ln(T / K ) Na + , K + :Cl L1Na + ,K + :Cl = 1639
Alkali sulfide solid solution, Na2S-K2S:
Two sublattices:
Cationic sublattice, C, two sites: Anionic sublattice,A, one site:
K+, Na+ S2-
1 1 o o C A C A C C C C e G m /( J mol 1 ) = y Na /( J mol 1 ) + y K ) + 2 RT ( y Na + yK ) + y 2 G + y 2 G + 2 /( J mol + ln y + ln y + ) + Gm /( J mol S Na + :S 2 S K :S Na + K 1 o o G Na ) = G Na /( J mol 1 ) + 2 /( J mol :S 2S ( s ) 1 o o GK ) = GK /( J mol 1 ) + 2 /( J mol :S 2S ( s ) 0 e C C A Gm /( J mol 1 ) = y Na + y + y 2 L K S Na + , K + :S 2
L0 = 26777.6 Na + , K + :S 2
Alkali disulfide solid solution, Na2S2-K2S2:
Two sublattices:
Cationic sublattice, C, two sites: Anionic sublattice,A, one site:

2 2 2
K+, Na+ S222
o o 1 1 C A C A C C C C e G m /( J mol 1 ) = y Na /( J mol 1 ) + y K ) + 2 RT ( y Na + yK ) + y 2 G + y 2 G + 2 /( J mol + ln y + ln y + ) + Gm /( J mol S Na + :S 2 S K :S Na + K
o 2 Na + :S 2
/( J mol ) = G
o Na2 S 2 ( s )
/( J mol )
o o 1 GK ) = GK /( J mol 1 ) + 2 /( J mol :S 2S2 ( s )

2
0 C C A G /( J mol 1 ) = y Na + y + y 2 L K S Na + , K + :S 2 e m
2 2
0 2 Na + , K + :S 2
= 26777 .6
Hexagonal solid solution, Na2CO3-Na2SO4-Na2S-K2CO3-K2SO4-K2S:
Two sublattices:
Cationic sublattice, C, two sites: Anionic sublattice, A, one site:

3 3 3
K+, Na+ CO32-, SO42-, S23 4 4
C A C A C A o o o G m /( J mol 1 ) = y Na G Na /( J mol 1 ) + y K GK /( J mol 1 ) + y Na G Na /( J mol 1 ) + y + + y + + y + SO 2 CO 2 CO 2 :CO 2 :CO 2 :SO 2
+y
C K+
y
3
A 2 SO 4
o 2 K + :SO 4
/( J mol ) + y
4 4
C Na +
A S 2
o Na + :S 2
/( J mol ) + y
C K+
A S 2
o K + :S 2
C C C C /( J mol ) + RT ( 2 ( y Na + yK + ln y + ln y + ) Na + K
A A A A e + ( y CO + y SO + y SA2 ln y SA2 )) /( J mol 1 ) + G m /( J mol 1 ) 2 ln y 2 ln y CO 2 SO 2

3
o 2 Na + :CO 3
/( J mol ) = G
o Na 2 CO 3 ( s , )
/( J mol 1 )
o o GK /( J mol 1 ) = G K /( J mol 1 ) + :CO 2 2 CO 3 ( s , )

3
o 2 Na + :SO 4
4
o /( J mol 1 ) = G Na /( J mol 1 ) 2 SO 4 ( s , I )
o o GK /( J mol 1 ) = G K /( J mol 1 ) + :SO 2 2 SO 4 ( s , )
o Na + :S 2
o /( J mol 1 ) = G Na /( J mol 1 ) + 16736 .0 2 .8033 (T / K ) 2S ( s )
1 o o GK ) = GK /( J mol 1 ) + 32925 .15 23 .2146 (T / K ) + 2 /( J mol :S 2S ( s ) e C A A A A A C A Gm /( J mol 1 ) = y Na y A ( L0 + L1Na + :CO 2 ,SO 2 ( y CO ) /( y CO )) + y K y A ( L0 + y 2 y 2 + y + y CO 2 SO 2 Na + :CO 2 , SO 2 SO 2 SO 2 CO 2 SO 2 K + :CO 2 , SO 2
3 4 3 4 3 4 3 4 3 4 3 4 3 4
+L
1 2 2 K + :CO 3 , SO 4
(y
4
A 2 CO 3
A 2 SO 4
) /( y
A 2 CO 3
+y
3
A 2 SO 4
)) + y
C K+
A 2 SO 4
A S 2
0 2 K + :S 2 , SO 4
+y
4
C Na +
C K+
A 2 CO 3
(L
4
0 2 Na + , K + :CO 3
+L
1 2 Na + , K + :CO 3
(y
C K+
C y Na + ))
C C A C C C C A + y Na ( L0 + L1Na + , K + :CO 2 ( y K )) + y Na y A L0 + y + y + y + y + y K SO 2 Na + , K + :SO 2 Na + K CO 2 SO 2 Na + , K + :CO 2 , SO 2

4 3 3
0 2 2 Na + :CO 3 , SO 4
= 4910
L1Na + :CO 2 ,SO 2 = 1590

3 4
L0 = 4872.5 K + :CO 2 , SO 2
3 4
1 2 2 K + :CO3 , SO4
= 157.5
L0 = 9444.21 K + :SO 2 , S 2
4
0 2 Na + , K + :CO3
= 10417.52
L1Na + , K + :CO 2 = 4392.36

3
0 2 Na + , K + :SO4
= 12577.5 4.686(T / K )
L1Na + , K + :SO 2 = 3556.4 4.686(T / K )

4
0 2 2 , SO4 Na + , K + :CO3
= 1401.272
Na2SO4-rich low-temperature solid solution, Na2CO3-Na2SO4-K2CO3-K2SO4:
Two sublattices:

3 3 3
K+, Na+ CO32-, SO423 4 4 4 4
C A C A C A C A G m /( J mol 1 ) = y Na Go /( J mol 1 ) + y K Go /( J mol 1 ) + y Na Go /( J mol 1 ) + y K Go /( J mol 1 ) + y + y + y + y CO 2 Na + :CO 2 CO 2 K + :CO 2 SO 2 Na + :SO 2 SO 2 K + :SO 2
+ RT (2( y
3
C Na +
ln y
C Na +
+y
C K+
ln y ) + ( y
C K+
A 2 CO3
ln y
A 2 CO3
+y
A 2 SO4
ln y
A 2 SO4
)) /( J mol ) + G /( J mol )
e m
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + 7112.8 + :CO 2 2CO3 ( s , )
o 2 K + :CO3
o /( J mol 1 ) = GK /( J mol 1 ) + 4184 2CO3 ( s , )
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + :SO 2 2 SO4 ( s , IV )

4
o 2 K + :SO4
o /( J mol 1 ) = GK /( J mol 1 ) + 33472 2 SO4 ( s , )
e C A Gm /( J mol 1 ) = y Na y A L0 + y CO 2 SO 2 Na + :CO 2 , SO 2
3 4 3 4
0 2 2 ,SO4 Na + :CO3
= 3347.2
K2SO4-rich, low-temperature orthorhombic solid solution, Na2CO3-Na2SO4-K2CO3-K2SO4:
Two sublattices:

3 3 3
K+, Na+ CO32-, SO423 4 4 4 4
+ RT (2( y
3
C Na +
ln y
C Na +
+y
C K+
ln y ) + ( y
C K+
A 2 CO3
ln y
A 2 CO3
+y
A 2 SO4
ln y
A 2 SO4
)) /( J mol ) + G /( J mol )
e m
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + 20920 + :CO 2 2CO3 ( s , )
o 2 K + :CO3
o /( J mol 1 ) = GK /( J mol 1 ) + 209.2 2CO3 ( s , )
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + 29288 20.92(T / K ) + :SO 2 2 SO4 ( s , IV )

4
o 2 K + :SO4
o /( J mol 1 ) = GK /( J mol 1 ) 2 SO4 ( s , )
e C A A A Gm /( J mol 1 ) = y K y A ( L0 + L1K + :CO 2 ,SO 2 ( yCO )) + y 2 y CO 2 SO 2 K + :CO 2 , SO 2 SO 2

3 4 3 4 3 4 3 4
0 2 2 K + :CO3 , SO4
= 3765.6
L1K + :CO 2 ,SO 2 = 2008.32

3 4
Na2CO3-rich, low temperature solid solution, Na2CO3-Na2SO4-K2CO3-K2SO4:
Two sublattices:
K+, Na+ CO32-, SO423 3 4 4 4 4

3 3
+ RT (2( y
3
C Na +
ln y
C Na +
+y
C K+
ln y ) + ( y
C K+
A 2 CO3
ln y
A 2 CO3
+y
A 2 SO4
ln y
A 2 SO4
)) /( J mol ) + G /( J mol )
e m
o o G Na /( J mol 1 ) = G Na /( J mol 1 ) + :CO 2 2CO3 ( s , )
o 2 K + :CO3
o /( J mol 1 ) = GK /( J mol 1 ) + 1255.2 2CO3 ( s , )
o o G Na /( J mol 1 ) = G Na /( J mol 1 ) + 5522.88 + :SO 2 2 SO4 ( s , IV )

4
o 2 K + :SO4
o /( J mol 1 ) = GK /( J mol 1 ) + 4184 2 SO4 ( s , )
e C C A C C Gm /( J mol 1 ) = y Na ( L0 + L1Na + , K + :CO 2 ( y K )) + y + y + y K CO 2 Na + , K + :CO 2 Na +

3 3 3
0 2 Na + , K + :CO3
= 10460
L1Na + , K + :CO 2 = 4184

3
Na2CO3-rich, very-low temperature solid solution, Na2CO3-Na2SO4-K2CO3-K2SO4:
Two sublattices:

3 3 3
K+, Na+ CO32-, SO423 4 4 4 4
+ RT (2( y
C Na +
ln y
C Na +
+y
C K+
ln y ) + ( y
C K+
A 2 CO3
ln y
A 2 CO3
+y
A 2 SO4
ln y
A 2 SO4
)) /( J mol ) + G /( J mol )
e m
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + :CO 2 2CO3 ( s , )

3
o 2 K + :CO3
o /( J mol 1 ) = GK /( J mol 1 ) + 1882.8 2CO3 ( s , )
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + 5690.4 + :SO 2 2 SO4 ( s , IV )

4
o 2 K + :SO4
o /( J mol 1 ) = GK /( J mol 1 ) + 4184 2 SO4 ( s , )
e C C A C C Gm /( J mol 1 ) = y Na ( L0 + L1Na+ ,K + :CO2 ( y Na + y + y + y + )) K CO 2 Na + , K + :CO 2 K

3 3 3
0 2 Na + , K + :CO3
= 10460
L1Na + ,K + :CO2 = 4184

3
K2CO3-rich, low-temperature solid solution, Na2CO3-Na2SO4-K2CO3-K2SO4:
Two sublattices:
K+, Na+ CO32-, SO423 3 4 4 4 4

3 3
+ RT (2( y
3
C Na +
ln y
C Na +
+y
C K+
ln y ) + ( y
C K+
A 2 CO3
ln y
A 2 CO3
+y
A 2 SO4
ln y
A 2 SO4
)) /( J mol )
o o GNa /( J mol 1 ) = G Na /( J mol 1 ) + 9100.2 3.3472(T / K ) + :CO 2 2CO3 ( s , )
o 2 K + :CO3
o /( J mol 1 ) = GK /( J mol 1 ) 2CO3 ( s , )
o o GNa /( J mol 1 ) = GNa /( J mol 1 ) + 11757.04 + :SO 2 2 SO4 ( s , IV )

4
o 2 K + :SO4
o /( J mol 1 ) = GK /( J mol 1 ) + 7238.32 2 SO4 ( s , )
Glaserite, K3Na(SO4)2-Na3(Na)(SO4)2:
Three sublattices:
Cationic sublattice 1, C1, three sites: K+, Na+ Cationic sublattice 2, C2, one site: Na+ Anionic sublattice, A, two sites: SO424 4 4 4
1 C1 C 2 C1 C2 C1 C1 C1 C1 G m /( J mol 1 ) = yK y A Go /( J mol 1 ) + y Na y A Go /( J mol 1 ) + 3RT ( y Na + yK ) + y + y + ln y + ln y + ) /( J mol Na + SO2 K + :Na+ :SO2 Na+ SO2 Na+ :Na+ :SO2 Na+ K
o 2 K + :Na+ :SO4
/( J mol ) = 1.5G
o K 2 SO4 ( s , )
/( J mol ) + 0.5G
o Na2 SO4 ( s , I )
/( J mol ) 10878.4 + 9.7906(T / K )
o o GNa /( J mol 1 ) = 2GNa /( J mol 1 ) + 16736 10.711(T / K ) + :Na + :SO2 2 SO4 ( s , I )

4
Na-rich alkali disulfate Na2S2O7-K2S2O7:
Two sublattices:
Cationic sublattice, C, two sites: K+, Na+ Anionic sublattice, A, one site: S2O72o 1 C A C A C C C C G m /( J mol 1 ) = y Na G Na /( J mol 1 ) + y K Go /( J mol 1 ) + 2 RT ( y Na + yK ) + y + + y + ln y + ln y + ) /( J mol :S O 2 S O2 S O 2 K + :S O 2 Na + K
2 7 2 7 2 7 2 7
o 2 Na + :S 2O7
/( J mol ) = G
o Na2 S 2O7 ( s )
/( J mol )
o o GK /( J mol 1 ) = G K /( J mol 1 ) + 29288 + :S O 2 2 S 2O7 ( s , )

2 7
K-rich alkali disulfate Na2S2O7-K2S2O7:
Two sublattices:
Cationic sublattice, C, two sites: K+, Na+ Anionic sublattice, A, one site: S2O721 o o C A C A C C C C G m /( J mol 1 ) = y Na G Na /( J mol 1 ) + y K GK /( J mol 1 ) + 2 RT ( y Na + yK ) + y + + y + + ln y + ln y + ) /( J mol :S O 2 :S O 2 S O 2 S O 2 Na + K
2 7 2 7 2 7 2 7
o 2 Na + :S 2O7
/( J mol ) = G
o Na2 S 2O7 ( s )
/( J mol ) + 26777.6 32.8193(T / K )
o o GK /( J mol 1 ) = G K /( J mol 1 ) + :S O 2 2 S 2O7 ( s , )

2 7
Appendix C. Interaction parameters for the liquid phase in binary, ternary common-ion and ternary reciprocal systems. Binary systems
Na-S
g NaNa / SS 2 /( J mol 1 ) = 2510.4 NaNa / SS 2
g NaNa / SVa /( J mol 1 ) = 19664.8 6.6944(T / K )
K-S Na-K* Na2CO3-Na2SO4 Na2CO3-Na2S Na2SO4-Na2S Na2SO4-Na2S2O7 NaCl-Na2SO4 NaCl-Na2CO3 K2CO3-K2SO4 K2CO3-K2S K2SO4-K2S K2SO4-K2S2O7 KCl-K2SO4 KCl-K2CO3 Na2CO3-K2CO3 Na2SO4-K2SO4 Na2S2O7-K2S2O7 NaCl-KCl
g KK / SVa /( J mol 1 ) = 8996 0.837(T / K ) + 627.6 KK / SVa + 627.6( KK / SVa )2

g NaK / VaVa /( J mol 1 ) = 750.37 + 0.2103(T / K ) + (468.61 0.4335(T / K ) )YNa
2 3 1.6986(T / K )YNa + 1.9508(T / K )YNa
g Na2 / CO3SO4 /( J mol 1 ) = 385.2
g Na 2 / CO3 S /( J mol 1 ) = 2092.0 + 2217.5 Na 2 / SCO3 2092.0 Na 2 / CO3 S g Na2 / SSO4 /( J mol 1 ) = 1790.75
g Na2 / SO4 S2O7 /( J mol 1 ) = 1223.0 g Na2 / ClSO4 /( J mol 1 ) = 276.1
g Na 2 / ClCO3 /( J mol 1 ) = 276.1 186.9 Na 2 / ClCO3 g K2 / CO3SO4 /( J mol 1 ) = 251.0 g K2 / CO3S /( J mol 1 ) = 2011.7 g K 2 / SSO4 /( J mol 1 ) = 6258.4 g K 2 / SO4 S 2 O7 /( J mol 1 ) = 6376.4 + 7.042(T / K ) g K 2 / ClSO4 /( J mol 1 ) = 412.1 + 571.1 K 2 / ClSO4
g K 2 / ClCO3 /( J mol 1 ) = 496.9 + 1665.2 K 2 / CO3Cl g NaK /(CO3 ) 2 /( J mol 1 ) = 1714.9 354.1 NaK /(CO3 ) 2
g NaK /( SO4 ) 2 /( J mol 1 ) = 1419.6 g NaK /( S 2 O7 ) 2 /( J mol 1 ) = 1623.4 g NaK / Cl 2 /( J mol 1 ) = 695.5 67.0 NaK / Cl 2
Ternary common-ion systems

KCl-K2CO3-K2SO4
001 gK /( J mol 1 ) = 1882.8 2 / ClSO4 ( CO3 )
Ternary reciprocal systems

Na2CO3-Na2SO4-K2CO3-K2SO4 NaCl-Na2SO4-KCl-K2SO4 NaCl-Na2CO3-KCl-K2CO3 *YNa =xNaNa/VaVa+1/2 xNaK/VaVa g NaK / SO4CO3 /( J mol 1 ) = 640.15
g NaK / ClSO4 /( J mol 1 ) = 619.2 5866.0 x Na2 /( SO4 )2 g NaK / ClCO3 /( J mol 1 ) = 1882.8
RECENT REPORTS FROM THE COMBUSTION AND MATERIALS CHEMISTRY GROUP OF THE ABO AKADEMI PROCESS CHEMISTRY CENTRE:
02-1 02-2 02-3 02-4 02-5 02-6 02-7
E. Coda Zabetta, P. Kilpinen, H. Pokela Ulla Koponen Mikael Bergelin J. Konttinen, S. Kallio, P. Kilpinen Johan Werkelin Edgardo Coda Zabetta Kristoffer Sandelin
CFD Testing of an Improved Model for Simulating NOx in Internal Combustion Engines Surface Electrochemistry of Ru- and Os- Modified Pt Electrodes The Impinging-Jet Flow-Cell as Measurement Tool in Interfacial Electrochemistry Oxidation of a Single Char Particle - Extension of the Model and Re-Estimation of Kinetic Rate Constants Distribution of Ash-Forming Elements in Four Trees of Different Species Modelling of Nitrogen Oxides in Combustion at Atmospheric and Elevated Pressures: Application to Biomass- and Oil-Derived Gaseous Fuels Chemical Equilibrium Studies on Trace Elements and on Two Process Problems in Solid Fuel Combustion Chemistry of HCl and Limestone in Fluidised bed combustion Char bed processes in a kraft recovery boiler - A CFD based study Development of phases and structures during pelletizing of Kiruna magnetite ore Conversion Kinetics for Smelt Anions: Cyanate and Sulfide
04-01 04-02 04-03 04-04
J. Partanen N. Bergroth Veikko Niiniskorpi Nikolai DeMartini
RECENT REPORTS FROM THE COMBUSTION AND MATERIALS CHEMISTRY GROUP OF THE ABO AKADEMI PROCESS CHEMISTRY CENTRE:
Edgardo Coda Zabetta, Mikko Hupa 05-02 J. Konttinen, R. Backman, M. Hupa, A. Moilanen, E. Kurkela 05-03 Edgardo Coda Zabetta, Clifford Ekholm, Mikko Hupa, Tommi Paanu, Mika Laurn, Seppo Niemi 05-04 Vesna Barii 05-01 Gas-born carbon particles generated by combustion: a review on the formation and relevance Trace element behaviour in the fluidized bed gasification of solid recovered fuels -A thermodynamic study TEKES FINE-BioPM Dieselmoottorin nanohiukkaspstt biopohjaisia ljyj poltettaessa (Nanoparticles from diesel engines operated with bio-derived oils)-Project report Morphology and composition of bed-material particles from combustion of biomass fuels and wastes in CFB boilers Gas-phase detailed chemistry kinetic mechanism A a mechanism, for simulating biomass conversion including methanol and nitrogen pollutants-validation, verification and parametric tests Interaction of Biomass Fly Ashes with Different Fouling Tendencies TGA-Investigation of KCl-kaolinite interaction Catalytic Reactions of N2O and NO over Bed Materials from Multifuel Circulating Fluidized Bed Combustion Sulphation of solid KCl
06-01 06-02 06-03 07-01 07-02
Edgardo Coda Zabetta Mischa Theis Michal Glazer Vesna Barisisc Andrius Gudzinskas, Johan Lindholm and Patrik Yrjas
ISSN 1459-8205 ISBN 978-952-12-1886-6 bo Akademis tryckeri bo, Finland, 2007

Thermochemistry of Salts 0703

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Thermochemistry of Salts 0703

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BO AKADEMI

TEKNISKA FAKULTETEN Processkemiska Centret FACULTY OF TECHNOLOGY Process Chemistry Centre

Academic Dissertation Laboratory of Inorganic Chemistry

bo, February 2007

Chapter 1- Introduction 1. Introduction

Weak black liquor

Flue gases Steam Electricity

1.1 Objective of the study

Chapter 2-Alkali salts in the recovery boiler

Na2S(l) + 2 O2(g) Na2SO4(l)

Chapter 2-Alkali salts in the recovery boiler

Na2CO3(s,l) + X C(s) 2 Na(g) + (2X-1) CO(g) + (2-X) CO2(g) [0.5X2].

Chapter 2-Alkali salts in the recovery boiler

3.1 Overview of the properties of ionic compounds and solutions

Chapter 3-Thermodynamic modeling

3.2 Thermodynamic equilibrium modeling

Chapter 3-Thermodynamic modeling

where ni is the amount of component i, or alternatively by

Chapter 3-Thermodynamic modeling

3.3 Optimization of phase diagrams and thermodynamic data

Chapter 3-Thermodynamic modeling 3.4 Thermodynamic models of ionic solutions

3.4.1 Ideal solutions

Chapter 3-Thermodynamic modeling

The Gibbs energy of mixing is therefore given by the following expression:

The molar Gibbs energy of an ideal solution is

3.4.2 Nonideal solutions

Chapter 3-Thermodynamic modeling

[Eq. 3.9.1] [Eq. 3.9.2] [Eq. 3.9.3]

Chapter 3-Thermodynamic modeling

n where the term ij is a binary interaction parameter dependent on the value of n.

3.4.3 Sublattice models

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

3.4.4 Compound Energy Formalism

S T o S T S T o S T o o Gm = y A yC GA:C + y A yDGA : D + y B yC GB:C + y B y D GB: D S S S S T T T T + (mRT ( y A ln y A + yB ln yB ) + nRT ( yC ln yC + yD ln yD )) + G E .

Chapter 3-Thermodynamic modeling

S S T S S T S T T S T T S S T T G E = yA y B yC LA,B:C + y A yB yD LA,B:D + y A yC yD LA:C ,D + y B yC yD LB:C ,D + y A yB yC yD LA,B:C ,D

3.4.5 Modified Quasichemical Model in the Quadruplet Approximation

Chapter 3-Thermodynamic modeling

[K CO3 ]pair + [Na Cl ]pair = [K Cl ]pair + [Na CO3 ]pair

g K , Na / CO3 ,Cl . [Eq. 3.20] g Na , K / SO4 , [Eq. 3.21.1] g Na / CO3 , SO4 .

[Na SO4 Na ]pair + [K SO4 K ]pair = 2[Na SO4 K ]pair

[CO3 Na CO3 ]pair + [SO4 Na SO4 ]pair = 2[CO3 Na SO4 ]pair

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

Pelton et al. [17] (Equations 46-48 in reference [17]).

Chapter 3-Thermodynamic modeling

xA/ X x + nB / X ln B / X YAYX YBYX

xA / X2 xB / X 2 xA/Y x + nB / Y ln B / Y ) + ( n A2 / X 2 ln 4 2 2 + n A2 / X 2 ln 4 2 2 + 2 YAYY YBYY x A / X /(YA YX ) xB / X /(YB YX2 ) x A2 / Y2

x AB / XY ) 4 x A / X xB / X x A / X x B / Y /(YAYBYX YY ) [Eq. 3.28]

Chapter 3-Thermodynamic modeling

[Eq. 3.30.1] [Eq. 3.30.2] [Eq. 3.30.3] [Eq. 3.30.4]

Chapter 3-Thermodynamic modeling

3.4.6 Extrapolation of excess Gibbs energy in multicomponent solutions

Chapter 3-Thermodynamic modeling

[Eq. 3.34] Muggianu/Toop approximation: G E = x A xB ( L0AB + L1AB ( x A xB xC ) + x A xC ( L0AC + L1AC ( x A xC xB ))

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

Chapter 3-Thermodynamic modeling

48116 n + 2 n 25104 2 k (k 1) + 4.184 n (T / K )

Chapter 3-Thermodynamic modeling