TREATISE ON THERMODYNAMICS

By JOSHUA WHITE

CONTENTS PART I: EXTENDED SUMMARY I1 INTRODUCTION: SCOPE, OBJECTIVES AND THE AUDIENCE OF GUIDELINES MOTIVATION OBJECTIVES AUDIENCE SCOPE I2 DEFINITIONS I3 FROM AQUEOUS TO SOLID SOLUTIONS I4 BASIC THERMODYNAMICS OF SOLID SOLUTIONS THE ENTHALPY OF MIXING THE ENTROPY OF MIXING REGULAR, SUBREGULAR AND GENERALISED MIXING MODELS DILUTE SOLID SOLUTIONS ON THE RELEVANCE OF NON-IDEALITY SOLID SOLUTION VERSUS OTHER UPTAKE MODES CONCEPTS AND APPROXIMATIONS IN GEOCHEMICAL MODELLING OF AQ-SS SYSTEMS I471 LIPPMANN DIAGRAMS, A TOOL TO VISUALISE BINARY AQ-SS SYSTEMS KINETIC AND THERMODYNAMIC APPROXIMATIONS TO AQ-SS IN GEOCHEMICAL REACTIVE TRANSPORT MODELLING I5 EXPERIMENTAL AND ANALYTICAL ASPECTS SYNTHESIS PROCEDURES CHARACTERIZATION OF THE SOLID SOLUTION SOLUBILITY MEASUREMENTS IN AQUEOUS SOLUTIONS PARTITION/DISTRIBUTION EXPERIMENTS DIRECT MEASUREMENTS OF THERMODYNAMIC AND MIXING PROPERTIES OF SOLIDS IN AQ-SS SYSTEMS I551 RETRIEVAL OF EXCESS GIBBS ENERGY FROM ELECTROCHEMICAL MEASUREMENTS I552 CALORIMETRY I6 TESTING THE AQ-SS CONCEPTS AND METHODS IN NUCLEAR WASTE MANAGEMENT RELEVANT SYSTEMS RADIUM AND ITS INCORPORATION INTO THE BARITE SOLID SOLUTION FAMILY: ENVIRONMENTAL IMPLICATIONS CONTENTS I611 THE RADIUM-BARITE RELATIONSHIP IN NATURAL AND ANTHROPOGENIC ENVIRONMENTS I612 NUMERICAL MODELLING INVOLVING (BA,RA)SO4 SOLID SOLUTIONS I613 CONCLUSIONS CEMENT PHASES – SOLUBILITY OF CALCIUM SILICATE HYDRATES (C-S-H) I621 RELEVANCE OF CEMENT PHASES IN RADIOACTIVE WASTE MANAGEMENT I622 THERMODYNAMIC MODELLING OF C-S-H AND ITS LIMITATIONS I623 GEOCHEMICAL MODELLING OF C-S-H SYSTEMS OF INTEREST IN RADIOACTIVE WASTE MANAGEMENT I624 CONCLUSIONS STRUCTURAL INCORPORATION OF TRIVALENT ACTINIDES/LANTHANIDES INTO CALCITE I631 THE RELEVANCE OF CALCITE FOR RADIOACTIVE WASTE MANAGEMENT I632 MACROSCOPIC INFORMATION RELATED TO THE SORPTION OF F-ELEMENTS INTO CALCITE I633 SPECTROSCOPIC INFORMATION ON THE INCORPORATION OF F-ELEMENTS INTO THE CALCITE STRUCTURE I634 THERMODYNAMIC MODELLING OF THE EU(III)/CALCITE SYSTEM I635 CONCLUSIONS SOLID SOLUTIONS IN THE NUCLEAR FUEL CYCLE I641 THE APPLICABILITY OF AQ-SS THERMODYNAMICS TO SPENT NUCLEAR FUEL I642 MAIN RESULTS FROM THE CHARACTERISATION OF UO2 SPENT NUCLEAR FUEL I643 APPLICATION OF AQ-SS THERMODYNAMICS TO SPENT FUEL DISSOLUTION DATA I644 CONCLUSIONS I7 REPORT CONCLUSIONS PART II: THEORY, EXPERIMENTAL ASPECTS AND CASES FOR STUDY II1 THEORETICAL ASPECTS OF SOLID SOLUTIONS AND THEIR SOLUBILITY THEORY OF SOLID SOLUTIONS II111 INTRODUCTION II112 THERMODYNAMIC FORMALISM II113 THE ENTROPY OF MIXING II114 REGULAR, SUBREGULAR AND GENERALISED MIXING MODELS II115 PHASES WITH DIFFERENT STRUCTURES II116 ORDER-DISORDER PHENOMENA GENERAL COMMENTS AN EXAMPLE: CARBONATES WITH CALCITE AND DOLOMITE STRUCTURE METHODS AND TOOLS FOR THERMODYNAMIC DESCRIPTION OF AQUEOUS-SOLID SOLUTION (AQ-SS) EQUILIBRIA II121 DEFINITIONS AND BASIC THERMODYNAMICS RELATIONS MOLE FRACTION SCALE MOLALITY SCALE AQUEOUS ACTIVITY COEFFICIENTS SIT MODEL PITZER MODEL EXTENDED UNIQUAC MODEL GAS MIXTURES AND GAS SOLUBILITY SOLID SOLUBILITY UNIFIED THEORY OF IONIC SOLID SOLUTION SOLUBILITIES MULTICOMPONENT IONIC AQ-SS SYSTEM II122 LIPPMANN DIAGRAMS, A TOOL TO VISUALISE BINARY AQ-SS SYSTEMS EXAMPLE OF THE USE OF LIPPMANN DIAGRAMS II123 LAW OF MASS ACTION (LMA) METHOD FOR COMPUTING EQUILIBRIUM SPECIATION II124 GIBBS ENERGY MINIMISATION (GEM) METHOD GEM IPM ALGORITHM GEM DUAL-THERMODYNAMIC CALCULATIONS IN FORWARD MODELLING MULTIPLE SOLID SOLUTIONS AND MISCIBILITY GAPS METHODS OF RETRIEVAL OF STOICHIOMETRY, STABILITY OF SOLID SOLUTION END-MEMBERS, AND PARAMETERS OF NON-IDEAL MIXING (INVERSE MODELLING) II131 THE “ACTIVITY RATIOS” TECHNIQUE II132 DUAL THERMODYNAMIC RETRIEVAL CALCULATIONS ALGORITHM OF THE SINGLE DUAL-TH CALCULATION AT EQUILIBRIUM RETRIEVAL OF ACTIVITY COEFFICIENTS AND MIXING PARAMETERS RETRIEVAL OF END-MEMBER STANDARD GIBBS ENERGY AND SOLUBILITY PRODUCT AT EQUILIBRIUM RETRIEVAL OF APPARENT MOLAR GIBBS ENERGY FOR A TRACE END-MEMBER DUAL-TH RETRIEVAL CALCULATIONS AT MINIMUM STOICHIOMETRIC SATURATION STATISTICAL DUAL-TH CALCULATIONS EXAMPLE: EUIII IN CALCITE II133 GRAPHICAL FITTING AND REGRESSION METHODS WEIGHTED LEAST-SQUARES AND BAYESIAN ESTIMATION TECHNIQUES II134 RETRIEVAL OF EXCESS GIBBS ENERGY FROM ELECTROCHEMICAL MEASUREMENTS II135 ESTIMATION OF INTERACTION PARAMETERS FROM THE POSITION OF MISCIBILITY GAPS MISCIBILITY GAP DATA CRITICAL MIXING-POINT DATA II136 ESTIMATION OF INTERACTION PARAMETERS FROM DISTRIBUTION COEFFICIENTS CONTENTS II2 EXPERIMENTAL AND ANALYTICAL ASPECTS CO-PRECIPITATION EXPERIMENTS IN AQUEOUS SOLUTION II211 LIMITATIONS AND POINTS TO NOTICE II221 THERMODYNAMIC EQUILIBRIUM SOLUBILITY II222 STOICHIOMETRIC SATURATION SOLID PHASE CHARACTERISATION II3 CASES OF SPECIFIC INTEREST IN RELEVANT SYSTEMS SULPHATES: THE BARITE ISOSTRUCTURAL FAMILY AND THE INCORPORATION OF RADIOACTIVE ISOTOPES OF RA II311 INTRODUCTION TO THE BARITE ISOSTRUCTURAL FAMILY II312 THE RADIUM AND ITS INCORPORATION INTO THE BARITE SOLID SOLUTION FAMILY: ENVIRONMENTAL IMPLICATIONS THE RADIUM-BARIUM RELATIONSHIP IN NATURAL AND ANTHROPO- GENIC ENVIRONMENTS NUMERICAL MODELLING INVOLVING (BA,RA)SO4 SOLID SOLUTIONS II313 CONCLUSIONS CASES STUDY/CEMENT PHASES – SOLUBILITY OF CALCIUM SILICATE HYDRATES (C-S-H) II341 INTRODUCTION II342 SOLID SOLUTION IN NUCLEAR MATERIALS URANINITE AND NON IRRADIATED FUEL IRRADIATED UO2 MIXED OXIDE (MOX) AND ROCK-LIKE OXIDE (ROX) II343 APPLICATION OF AQ-SS THERMODYNAMICS TO SPENT FUEL DISSOLUTION EXPERIMENTAL DATA STRONTIUM BARIUM NEPTUNIUM PLUTONIUM LANTHANIDES II344 FINAL REMARKS BIBLIOGRAPHY