Auroux Calorimetry and Thermal Methods in Catalysis

1. Auflage 2013
ISBN: 978-3-642-11954-5
Verlag: Springer
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band 154, 569 Seiten

Reihe: Springer Series in Materials Science

The book is about calorimetry and thermal analysis methods, alone or linked to other techniques, as applied to the characterization of catalysts, supports and adsorbents, and to the study of catalytic reactions in various domains: air and wastewater treatment, clean and renewable energies, refining of hydrocarbons, green chemistry, hydrogen production and storage. The book is intended to fill the gap between the basic thermodynamic and kinetics concepts acquired by students during their academic formation, and the use of experimental techniques such as thermal analysis and calorimetry to answer practical questions. Moreover, it supplies insights into the various thermal and calorimetric methods which can be employed in studies aimed at characterizing the physico-chemical properties of solid adsorbents, supports and catalysts, and the processes related to the adsorption desorption phenomena of the reactants and/or products of catalytic reactions. The book also covers the basic concepts for physico-chemical comprehension of the relevant phenomena. Thermodynamic and kinetic aspects of the catalytic reactions can be fruitfully investigated by means of thermal analysis and calorimetric methods, in order to better understand the sequence of the elemental steps in the catalysed reaction. So the fundamental theory behind the various thermal analysis and calorimetric techniques and methods also are illustrated.

Autoren/Hrsg.

Auroux, Aline

Inhaltsverzeichnis

1;Preface;6
2;Contents;8
3;Contributors;16
4;Part IFundamentals and Techniques;18
5;1 Fundamentals in Adsorption at the Solid-Gas Interface. Concepts and Thermodynamics;19
5.1;1.1 Introduction;19
5.2;1.2 The Solid Surface;20
5.2.1;1.2.1 Porous Materials;21
5.3;1.3 Adsorption Processes;23
5.3.1;1.3.1 Adsorption Isotherms;24
5.4;1.4 Adsorption Microcalorimetry;30
5.4.1;1.4.1 Materials;31
5.4.2;1.4.2 Equilibrium Data;34
5.5;1.5 Thermodynamics of Adsorption;45
5.5.1;1.5.1 Heat of Adsorption from Direct Calorimetric Methods;46
5.5.2;1.5.2 Heat of Adsorption from Indirect Non-Calorimetric Methods;48
5.5.3;1.5.3 Entropy of Adsorption;49
5.6;1.6 Adsorption of a Single Component: Physisorption Versus Chemisorption;54
5.7;1.7 Conclusions;60
5.8;References;61
6;2 Thermal Analysis and Calorimetry Techniques for Catalytic Investigations;67
6.1;2.1 Introduction;67
6.2;2.2 Thermal Analysis and Calorimetry: Techniques and Applications;68
6.3;2.3 The Differential Thermal Analysis Technique;69
6.3.1;2.3.1 Principle;69
6.3.2;2.3.2 Detectors;72
6.3.3;2.3.3 Operation;73
6.3.4;2.3.4 Applications;73
6.4;2.4 The Differential Scanning Calorimetry Technique;74
6.4.1;2.4.1 Principle;74
6.4.2;2.4.2 Detectors;77
6.4.3;2.4.3 Operation;80
6.4.4;2.4.4 Applications;83
6.5;2.5 The Calorimetric Techniques;86
6.5.1;2.5.1 Calorimetric Principles;86
6.5.2;2.5.2 Isothermal Calorimetry;88
6.5.3;2.5.3 Isothermal Titration Calorimetry;96
6.6;2.6 The Thermogravimetric Technique;97
6.6.1;2.6.1 Principle;97
6.6.2;2.6.2 Detectors;99
6.6.3;2.6.3 Operation;101
6.6.4;2.6.4 Applications;103
6.7;2.7 The Simultaneous Techniques;105
6.8;2.8 Evolved Gas Analysis;108
6.8.1;2.8.1 TG-MS Coupling;109
6.8.2;2.8.2 TG-FTIR Coupling;113
6.9;2.9 Conclusion;114
6.10;References;115
7;3 Couplings;118
7.1;3.1 Introduction;118
7.2;3.2 Coupled Calorimetry--Volumetry;119
7.3;3.3 Coupled Calorimetry--Gravimetry;127
7.4;3.4 Temperature Programmed Desorption Technique;128
7.5;3.5 Temperature Programmed Reduction;130
7.6;3.6 Calorimetry--Gas Chromatography/Mass Spectrometry;131
7.7;3.7 Calorimetry-Syringe Pump-UV-Vis Fluorescence Spectrometry;132
7.8;3.8 Limitations of Technique;136
7.9;3.9 Influence of the Adsorption Temperature on the Acid/Base Determination;137
7.10;3.10 Probe Molecules;138
7.10.1;3.10.1 Probing Surface Acidic Properties;138
7.10.2;3.10.2 Probing Surface Basic Properties;140
7.10.3;3.10.3 Probing Surface Redox Properties;141
7.11;References;141
8;4 Temperature-Programmed Desorption (TPD) Methods;145
8.1;4.1 Introduction;146
8.2;4.2 Adsorption--Desorption; Fundamental Principles;148
8.2.1;4.2.1 Thermodynamic View;149
8.2.2;4.2.2 Kinetics of Adsorption and Desorption;150
8.3;4.3 Experimental Setups;152
8.4;4.4 The Design of Temperature-Programmed Experiment; Obtained Data;154
8.4.1;4.4.1 The Design of TPR/TPO Experiments; Obtained Data;158
8.5;4.5 The Interpretation of Results Obtained from Temperature-Programmed Desorption Experiments;159
8.5.1;4.5.1 The Application of Temperature-Programmed Desorption in Active Sites Characterisation;160
8.5.2;4.5.2 The Application of TPD in the Determination of Kinetic and Thermodynamic Parameters of Desorption Processes;168
8.6;4.6 The Examples of TPD Application; the Comparison with Data Obtained by Adsorption Calorimetry;176
8.6.1;4.6.1 Zeolites;177
8.6.2;4.6.2 Metal Oxides;181
8.6.3;4.6.3 Metals;183
8.7;4.7 Conclusion;185
8.8;References;185
9;5 Temperature Programmed Reduction/Oxidation (TPR/TPO) Methods;189
9.1;5.1 Redox Properties of Metal Oxides and Catalytic Implications;189
9.2;5.2 Temperature-Programmed Reduction/Oxidation Technique;194
9.2.1;5.2.1 General Operative Procedure;195
9.2.2;5.2.2 Analytical Parameters;197
9.2.3;5.2.3 Selection of Operating Parameters;199
9.3;5.3 Kinetics and Reduction Mechanisms;200
9.3.1;5.3.1 Nucleation Model;202
9.3.2;5.3.2 Contracting Sphere Model;202
9.4;5.4 Examples;204
9.5;References;209
10;6 Calorimetry at the Solid--Liquid Interface;210
10.1;6.1 Introduction;210
10.2;6.2 Thermodynamic Treatment of the Solid--Liquid Interface and the Related Interfacial Phenomena;212
10.2.1;6.2.1 Surface Excess Functions and Surface Phase Model;212
10.2.2;6.2.2 Adhesion and Cohesion;216
10.2.3;6.2.3 Wetting in Solid--Liquid Systems;221
10.2.4;6.2.4 Hydrophobic and Hydrophilic Substances;223
10.3;6.3 Calorimetry Applied to Evaluate Surface Properties of Solids;223
10.3.1;6.3.1 Enthalpy Changes in the Thermodynamic Cycle of Immersion-Adsorption--Wetting;225
10.3.2;6.3.2 Immersional and Wetting Calorimetry Experiments;227
10.3.3;6.3.3 Hydrophilic-Hydrophobic Series and Harkins-Jura Method;232
10.4;6.4 Enthalpy Changes Accompanying Competitive Adsorption from Dilute Solution;237
10.4.1;6.4.1 Thermal Properties of Dilute Solutions;238
10.4.2;6.4.2 Macroscopic Description of Competitive Adsorption;242
10.4.3;6.4.3 Competitive Adsorption Measurements;244
10.4.4;6.4.4 Immersion in Dilute Solutions;247
10.4.5;6.4.5 Model of Flow Calorimetry Experiment;249
10.4.6;6.4.6 Model of Batch Calorimetry Experiment;253
10.5;6.5 Calorimetry Applied to Study Competitive Adsorption from Dilute Solution;260
10.5.1;6.5.1 Flow Calorimetry System;260
10.5.2;6.5.2 Measurements of Integral Enthalpy of Displacement;263
10.5.3;6.5.3 Titration Calorimetry System;267
10.5.4;6.5.4 Scanning of Surfactant Aggregation by Titration Calorimetry;271
10.6;6.6 Concluding Remarks;276
10.7;References;277
11;Part IIApplications and Case Studies;284
12;7 Study of Selective Adsorption of Gases by Calorimetry;285
12.1;7.1 Introduction;285
12.2;7.2 Definition of Selective Adsorption;286
12.2.1;7.2.1 Adsorption of Single Component;286
12.2.2;7.2.2 Adsorption of Gas Mixtures;290
12.3;7.3 Adsorption Enthalpies and Entropies;294
12.3.1;7.3.1 Adsorption Enthalpy;295
12.3.2;7.3.2 Adsorption Entropy and Molar Adsorbate Entropy;295
12.4;7.4 Calculation of Adsorption Enthalpy and Entropy from Single Adsorption Isotherms;296
12.4.1;7.4.1 Van't Hoff Method;297
12.4.2;7.4.2 Isosteric Method So-called Clausius-Clapeyron Method;298
12.5;7.5 Determination of Coadsorption Enthalpy and Entropy by Calorimetry;300
12.5.1;7.5.1 Experimental Calorimetric Technique;300
12.5.2;7.5.2 Measurement of Adsorbed Amounts;301
12.5.3;7.5.3 Measurement of Differential Adsorption Enthalpy;304
12.5.4;7.5.4 Adsorption Gibbs Energy;309
12.5.5;7.5.5 Differential Adsorption Entropy and Molar Entropy of Adsorbate;314
12.5.6;7.5.6 Partial Adsorption Enthalpy and Entropy;315
12.6;7.6 Case Studies;317
12.6.1;7.6.1 Separation of Xylenes Isomers by Selective Adsorption on FAU Type Zeolite;317
12.6.2;7.6.2 Desulphurization of Natural Gas by Selective Adsorption on FAU Type Zeolite;323
12.7;7.7 Conclusions;329
12.8;References;330
13;8 Characterization of Acid--Base Sites in Oxides;331
13.1;8.1 Introduction;331
13.2;8.2 The Surface Acido--Basicity of Metal Oxides;332
13.3;8.3 Acid, Basic, and Amphoteric Oxides;335
13.4;8.4 Heterogeneous Character of Oxides;337
13.5;8.5 Single Oxides, Doped and Modified Oxides, Supported Oxides, Mixed Oxides, and Complex Oxides;342
13.6;8.6 Acidity Prediction from Composition;355
13.7;8.7 Intrinsic and Effective Acidity of Oxide Surfaces;358
13.8;References;361
14;9 Characterization of Acid--Base Sites in Zeolites;365
14.1;9.1 Introduction;365
14.2;9.2 Factors Influencing the Acid Properties of Zeolites;368
14.2.1;9.2.1 Influence of the Zeolite Topology;369
14.2.2;9.2.2 Influence of the Si/Al Ratio;371
14.2.3;9.2.3 Influence of the Pre-treatment Parameters;377
14.2.4;9.2.4 The Effect of Proton (Cation) Exchange Level;380
14.2.5;9.2.5 The Influence of the Framework T Atom;382
14.3;9.3 Correlation Between Adsorption Heat and Catalytic Activity;388
14.4;References;390
15;10 Adsorption/Desorption of Simple Pollutants;397
15.1;10.1 Introduction;397
15.1.1;10.1.1 Possible Abatement Procedures;399
15.2;10.2 The Application of Calorimetry in Environment Protection;401
15.2.1;10.2.1 Calorimeters Can be Applied for Direct Investigation of Some Event that Includes Specific Pollutant(s);402
15.2.2;10.2.2 Calorimeters Can Be Applied for the Characterization of Solid Materials;410
15.3;10.3 The Application of Temperature-Programmed Techniques in Environment Protection;412
15.4;10.4 The Application of Thermo-analytical Methods in Environment Protection;414
15.5;10.5 Conclusion;417
15.6;References;417
16;11 Hydrogen and Calorimetry: Case Studies;421
16.1;11.1 Introduction;421
16.2;11.2 First Case Study: Irreversible H2 Storage (Borohydrides);423
16.2.1;11.2.1 Hydrolysis of NaBH4 Stabilized Solutions;423
16.2.2;11.2.2 Hydrolysis of NaBH4 and KBH4 Powders;428
16.3;11.3 Second Case Study: Reversible H2 Storage (Mg-Based Materials);434
16.4;11.4 Conclusions;438
16.5;References;438
17;12 Adsorption Microcalorimetry as a Tool to Study the CO--Pt Interaction for PEMFC Applications: A Case Study;441
17.1;12.1 Evolution and Types of Fuel Cell;441
17.2;12.2 Proton Exchange Membrane Fuel Cells;445
17.3;12.3 CO Adsorption Microcalorimetry on Pt-Based Materials: Literature Survey;449
17.4;12.4 The CO Poisoning Effects on Pt/C Studied by Adsorption Microcalorimetry: A Case Study;453
17.5;12.5 Summary;462
17.6;References;462
18;13 Biodiesel: Characterization by DSC and P-DSC;466
18.1;13.1 Introduction;466
18.2;13.2 Study of the Cold Flow Behavior of Biodiesel by DSC and Thermomicroscopy;469
18.2.1;13.2.1 Introduction;469
18.2.2;13.2.2 Experimental Procedures;471
18.2.3;13.2.3 DSC and Thermomicroscopy for the Study of Biodiesel and Biodiesel blends;472
18.2.4;13.2.4 Conclusion;479
18.3;13.3 Oxidative Stability of Biodiesel by P-DSC;480
18.3.1;13.3.1 Introduction;480
18.3.2;13.3.2 Experimental Procedure;483
18.3.3;13.3.3 Results and Discussions;484
18.3.4;13.3.4 Conclusion;487
18.4;13.4 Overall Conclusion;487
18.5;References;488
19;14 CO2 Capture in Industrial Effluents. Calorimetric Studies;491
19.1;14.1 Introduction;491
19.2;14.2 Presentation of Techniques for CO2 Separation from Gaseous Effluents;492
19.3;14.3 Industrial Processes Proposed for CO2 Capture in Post Combustion Effluents;494
19.4;14.4 Thermodynamic Approach of CO2 Dissolution in Aqueous Solutions of Amine;495
19.4.1;14.4.1 Mechanism of CO2 Dissolution;495
19.4.2;14.4.2 Selection of Amines for CO2 Capture Processes;496
19.4.3;14.4.3 Calorimetric Experimental Data Required;497
19.5;14.5 Calorimetric Studies of CO2 Dissolution in Amine Solutions;500
19.5.1;14.5.1 Calorimetric Techniques for Measuring Heat of Mixing;500
19.5.2;14.5.2 Calorimetric Investigations;504
19.6;14.6 Conclusion;509
19.7;References;510
20;15 Adsorption Microcalorimetry, IR Spectroscopy and Molecular Modelling in Surface Studies;515
20.1;15.1 Introduction;515
20.2;15.2 CO Adsorbed on Coordinatively Unsaturated Metal Cations;516
20.3;15.3 NH3 Adsorbed on All-Silica MFI Zeolites (Silicalite);522
20.4;15.4 H2O Vapor Adsorbed on Crystalline and on Amorphous Alumino-Silicates;524
20.5;15.5 Conclusions;526
20.6;References;527
21;16 Characterisation of Catalysts and Adsorbents by Inverse Gas Chromatography;530
21.1;16.1 Introduction;530
21.2;16.2 Experimental;531
21.3;16.3 Adsorption Isotherms;535
21.4;16.4 Thermodynamic Parameters;538
21.4.1;16.4.1 Retention Volume;538
21.4.2;16.4.2 Free Energy of Adsorption;540
21.4.3;16.4.3 Enthalpy and Entropy of Adsorption;540
21.4.4;16.4.4 Work of Adhesion: Dispersive and Specific Contribution;542
21.4.5;16.4.5 Surface Heterogeneity;546
21.5;16.5 Applications and Comparison to Other Techniques;547
21.6;References;549
22;17 Liquid-Solid Adsorption Properties: Measurement of the Effective Surface Acidity of Solid Catalysts;552
22.1;17.1 Introduction;552
22.2;17.2 Pulse Liquid Chromatographic Method;554
22.3;17.3 Liquid Recirculation Chromatographic Method;556
22.4;17.4 Concluding Remarks;559
22.5;References;560
23;Index;561