Adsorption Theory Modeling and Analysis Toth

✍ Scribed by Jozsef Toth

• Publisher: Marcel Dekker
• Year: 2002
• Tongue: English
• Leaves: 888
• Series: Surfactant Science Series, Volume 107
• Edition: 1st
• Category: Library

✦ Synopsis

Offers an overview of the recent theoretical and practical results achieved in gas-solid (G/S), liquid-solid (L/S), and gas-liquid (G/L) adsorption research.

✦ Table of Contents

Cover Page......Page 1
Title Page......Page 2
ISBN: 0824707478......Page 3
Preface......Page 4
Contents......Page 6
Contributors......Page 8
B. Derivation of the Gibbs Equation for Adsorption on the Free Surface of Liquids. Adsorption Isotherms......Page 10
C. Derivation of the Gibbs Equation for Adsorption on Liquid=Solid Interfaces. Adsorption Isotherms......Page 12
D. Derivation of the Gibbs Equation for Adsorption on Gas=Solid Interfaces......Page 15
E. The Differential Adsorptive Potential......Page 19
A. The Basic Phenomenon of Inconsistency......Page 21
B. Inconsistent G=S Isotherm Equations......Page 23
III. THE UNIFORM AND THERMODYNAMICALLY CONSISTENT TWO-STEP INTERPRETATION OF G=S ISOTHERM EQUATIONS APPLIED FOR HOMOGENEOUS SURFACES......Page 24
B. The Second Step: The Mathematical Treatment and the Connection Between the First and Second Steps......Page 25
C. The Uniform and Consistent Interpretation of the Modified Langmuir Equation, General Considerations......Page 27
D. The Uniform and Consistent Interpretation of the Modified Fowler–Guggenheim Equation......Page 31
E. The Uniform and Consistent Interpretation of the Modified Volmer Equation......Page 40
F. The Uniform and Consistent Interpretation of the Modified de Boer–Hobson Equation......Page 43
G. Physical Interpretation of Constants Kx Present in the Modified Isotherm Equations Applied to Homogeneous Surfaces......Page 45
H. Properties of the Function c(P) Corresponding to the Modified Langmuir, FG, Volmer, and BH Isotherm Equations......Page 49
A. The Tóth Equation......Page 50
B. The Modified Fowler–Guggenheim Equation Applied to Heterogeneous Surfaces (FT Equation)......Page 54
C. The Modified Volmer Equation Applied to Heterogeneous Surfaces (VT Equation)......Page 57
D. The Modified de Boer–Hobson Equation Applied to Heterogeneous Surfaces (BT Equation)......Page 58
E. The Mathematically Generalized Form of mL, mFG, mV, mBH, To´th, FT, VT, and BT Equations......Page 60
F. Applicability of the To´th Equation to all Isotherms of Type I Measured on Heterogeneous Surfaces......Page 63
G. Inapplicability of the To´th Equation to Isotherms of Type I Measured on Heterogeneous Surfaces......Page 65
H. Practical Application of the Function cðPÞ Corresponding to All Isotherms of Type I Measured on Heterogeneous Surfaces......Page 75
A. The Brunauer–Emmett–Teller Equation and Its Thermodynamical Properties......Page 77
B. Modifications of the BET Equation......Page 80
C. The Harkins–Jura Equation and Its Thermodynamical Properties......Page 82
D. The Cloud Model of Multilayer Adsorption......Page 84
VI. CALCULATION OF THE SPECIFIC SURFACE AREA OF ADSORBENTS......Page 89
A. Calculation of the Specific Surface Area from Isotherms of Type II Without and With the Monolayer Domain......Page 90
B. Calculation of the Specific Surface Area from Isotherms of Type I with a Multilayer Domain and Measured Below the Critical Temperature......Page 94
C. Calculation of the Specific Surface Area from Isotherms of Type I Without a Multilayer Plateau and Measured Below the Critical Temperature......Page 96
A. Consequences of the Calculations Made with Data of Isotherms of Type II Measured in a Narrower Domain of Equilibrium Relative Pressure......Page 102
B. Consequences of the Calculations Made with Data of Isotherms of Type I Measured in a Narrower Domain of Relative (or Absolute) Equilibrium Pressure......Page 107
REFERENCES......Page 112
I. INTRODUCTION......Page 114
II. FUNDAMENTALS......Page 115
A. General Formulation......Page 118
B. Adsorption of Gases......Page 120
C. Adsorption of Gas Mixtures......Page 134
D. Adsorption from Solution of Nonelectrolytes......Page 139
E. Adsorption from Binary Solutions......Page 140
IV. LATTICE MODELS......Page 145
A. Fundamentals......Page 149
B. Selected Applications......Page 152
A. Introductory Remarks......Page 157
B. Modeling of the Adsorbent Surface......Page 158
C. Monte Carlo Simulation of Adsorption......Page 160
A. Monolayer Films......Page 164
B. Multilayer Adsorption......Page 169
VIII. CONCLUDING REMARKS......Page 172
REFERENCES......Page 174
I. INTRODUCTION......Page 184
A. Dubinin–Stoeckli Method......Page 186
B. Jaroniec–Choma Method......Page 188
III. MODELS BASED ON STATISTICAL MECHANICS......Page 189
A. DFT Method......Page 191
B. Limitations of DFT and Suggestions for Improvement......Page 194
C. Molecular Simulation Techniques......Page 195
A. HK Methods......Page 198
B. Sensitivity of PSD Predictions to Physical Parameters......Page 202
C. Limitations of HK Models and Suggested Improvements......Page 204
D. Corrections to HK Methods......Page 205
V. SURVEY OF PSD TECHNIQUES USED IN LITERATURE......Page 208
VI. NOTATION......Page 213
Greek Letters......Page 216
REFERENCES......Page 217
4 Adsorption Isotherms for the Supercritical Region......Page 220
A. Surface and Adsorption......Page 221
III. ACQUISITION OF SUPERCRITICAL ADSORPTION ISOTHERMS......Page 223
A. Measurement of Gas=Solid Adsorption Equilibria......Page 224
B. Principal Factors Affecting Adsorption Measurements......Page 226
C. Generating Isotherms by Molecular Simulation of Adsorption......Page 227
A. Experimental Datasets of the Adsorption Equilibria for the Supercritical Region......Page 228
B. Determination of Gas-Phase State......Page 231
D. Determination of Isosteric Heat of Adsorption......Page 235
E. Construction of the Characteristic or Generalized Isotherm......Page 238
F. Determination of the Absolute Adsorption......Page 240
A. Introduction......Page 243
B. State of the Art of Isotherm Modeling......Page 244
C. A New Isotherm Equation Suitable for Supercritical Adsorption......Page 245
D. Illustration of Modeling Supercritical Isotherms......Page 247
A. Is High-Pressure Adsorption Endless in the Pressure Range?......Page 252
B. What to Do Next for Supercritical Adsorption Study?......Page 254
VII. NOTATION......Page 255
REFERENCES......Page 256
I. INTRODUCTION......Page 260
A. Electrostatic Interactions......Page 263
B. The Dispersion Interaction......Page 281
C. Superposition of Interactions and the Energy Profiles......Page 284
D. The Hydrodynamic Interactions......Page 289
A. Phenomenological Transport Equation......Page 308
B. Limiting Analytical Solutions......Page 310
C. Exact Numerical Results......Page 315
IV. NONLINEAR ADSORPTION REGIMES......Page 318
A. Limiting Theoretical Models......Page 319
A. Experimental Methods......Page 342
B. Linear Adsorption Regime......Page 345
C. Nonlinear Adsorption Regimes......Page 359
VI. CONCLUDING REMARKS......Page 372
LIST OF SYMBOLS......Page 375
Greek......Page 377
REFERENCES......Page 379
I. INTRODUCTION......Page 384
II. THERMODYNAMICS OF INTERFACES: THE CONCEPT OF THE ‘‘BLACK BOX’’......Page 385
A. General Conditions of Capillary Equilibrium......Page 390
B. Capillary Equilibrium in Porous Media......Page 391
C. Problems and Numerical Algorithms......Page 395
D. Calculation of the Surface Tension......Page 398
E. Phase Diagrams of Capillary Equilibrium......Page 399
F. The Multicomponent Kelvin Equation......Page 407
A. Overview of Possible Approaches......Page 415
B. Fundamentals of the Potential Theory of Adsorption......Page 418
C. Numerical Algorithms......Page 420
D. Testing the Potential Theory......Page 422
E. Potential Theory of Adsorption and Thermodynamics of Surface Excesses......Page 428
F. The Asymptotic Adsorption Equation......Page 432
REFERENCES......Page 437
I. INTRODUCTION......Page 442
II. OVERVIEW OF EXPERIMENTAL RESULTS......Page 443
A. Phase Diagrams for Rare Gases on Graphite......Page 448
III. PHYSISORPTION THEORY......Page 459
A. Classical Models......Page 460
B. Statistical Mechanics of Physisorption......Page 462
C. Virial Approximations......Page 464
D. Intermolecular Potentials......Page 467
E. Steele’s Theory of Monolayer Adsorption......Page 471
F. Theories Describing Phase Diagrams......Page 474
A. The Two-Dimensional Lennard–Jones Model......Page 476
B. Equations of State for 2D L-J Fluids......Page 484
C. Theoretical Adsorption Properties......Page 488
D. Comparison with Experimental Results......Page 494
E. Overview of Computer Simulations......Page 503
V. CONCLUSIONS AND REMARKS......Page 508
REFERENCES......Page 509
I. INTRODUCTION......Page 518
B. Choice of the Functional Space......Page 519
C. Solution of the Problem......Page 520
D. The Menu......Page 521
III. THE PROBLEM IN STATISTICAL THERMODYNAMICS: BOLTZMANN STATISTICS......Page 522
B. A Method Based on Fourier Transform......Page 523
A. Einstein Theory......Page 524
B. Debye Theory......Page 525
D. Montroll and the Ab Fine Problem......Page 526
A. The Local Isotherm......Page 527
B. The Integral Equation......Page 528
C. The Overall Isotherm......Page 529
E. The Ab Fine Problem......Page 530
A. Desorption Kinetics Under Nonisothermal Conditions: Thermal Desorption Spectrometry......Page 533
B. Desorption Kinetics in Isothermal Conditions......Page 534
C. The Experimental Desorption Kinetics......Page 537
D. Accounting for the Experimental Desorption Kinetics......Page 538
A. Mathematical Problems......Page 541
B. Physicochemical Problems......Page 542
REFERENCES......Page 543
II. STOCHASTIC PROCESS AND ITS APPLICATION......Page 546
A. Stochastic Process......Page 547
B. Application of Stochastic Process......Page 551
C. Comparison Between Deterministic and Stochastic Models......Page 552
A. Model Development......Page 553
B. Parameter Estimation......Page 555
C. Comparison Between Deterministic and Stochastic Solutions......Page 556
A. Model Development......Page 557
B. Parameter Estimation......Page 560
V. STOCHASTIC MODELING AND SIMULATION OF BISOLUTE BATCH ADSORBER IN THE CASE OF NONLINEAR ISOTHERM......Page 561
A. Model Development and Parameter Estimation......Page 562
B. Model Verification......Page 566
VI. SIMULATION OF A FIXED-BED ADSORBER WITH A STOCHASTIC MODEL IN THE CASE OF THE LINEAR ISOTHERM......Page 569
A. Model Description and Parameter Estimation......Page 570
C. Model Sensitivity and Verification......Page 573
D. Comparison Between Deterministic and Stochastic Solutions......Page 577
VIII. NOTATION......Page 578
REFERENCES......Page 580
I. ADSORPTION OF BINARY LIQUID MIXTURES ON SOLID SURFACES......Page 582
II. THE FREE ENTHALPY OF WETTING OF THE SOLID–LIQUID INTERFACE AND THE THICKNESS OF THE ADSORPTION LAYER......Page 587
III. ENTHALPY OF IMMERSION ON SOLIDS IN BINARY LIQUID MIXTURES......Page 588
IV. COMBINATION OF ADSORPTION EXCESS ISOTHERMS AND ENTHALPY ISOTHERMS: NEW WAY FOR DETERMINATION OF ADSORPTION CAPACITY......Page 591
A. U-Shaped Excess Isotherms and Enthalpy Isotherms......Page 593
B. S-Shaped Excess Isotherms and Enthalpy Isotherms......Page 596
C. The Linearized Functions Δ21/n1σ(n)=f(x1/n1σ(n))......Page 598
VI. THE CLASSIFICATION OF ENTHALPY ISOTHERMS [17–31,33]......Page 599
A. Heat of Wetting in Amorphous Silica Dispersion and on Zeolites......Page 601
B. Immersional Wetting on Nonswelling Clay Minerals......Page 602
C. Heat of Wetting on Swelling Clay Minerals......Page 604
D. Adsorption of n-Butanol from Water on Modified Silicate Surfaces......Page 606
A. Introduction......Page 613
B. The Lattice Model and Its Application to Multimolecular Adsorption......Page 615
C. The Bragg–Williams Approach......Page 618
D. Thermodynamical Description of Sublayers of Intermediate Position......Page 621
E. Exchange Adsorption Equilibrium in the Intermediate Sublayers......Page 623
F. Thermodynamical Characterization of the Contact Sublayer......Page 624
G. Adsorption Equilibrium in the Contact Sublayer......Page 625
H. Algorithm of Computation......Page 626
I. Adsorption in Perfect Mixtures (a=kT ¼ 0)......Page 627
J. Adsorption in Real Mixtures Far from Demixing (a=kT ¼ 1:4)......Page 629
K. Adsorption in Real Mixtures, Close to Demixing (a=kT ¼ 1:95)......Page 632
IX. CONCLUSIONS......Page 635
REFERENCES......Page 636
I. INTRODUCTION......Page 640
A. Experimental Methods......Page 642
B. Experimental Data Used in Inverse Modeling......Page 652
C. Technical Aspects of Modeling......Page 657
III. MODELS......Page 659
A. General Model Aspects......Page 660
B. General Aspects in the Choice of a Model......Page 668
C. Nonscientific Influences on the Choice of Models......Page 670
D. Use of Previously Published Model Parameters......Page 673
E. Specific Model Aspects......Page 678
IV. SPECIAL CASES......Page 705
A. Multiple Component Systems......Page 706
B. Surface Precipitation......Page 708
C. Temperature Dependence......Page 710
A. Data Acquisition......Page 712
B. Modeling Procedures......Page 714
REFERENCES......Page 716
I. INTRODUCTION......Page 720
A. Interaction of Solid with Water: Hydration, Hydrolysis, Dissolution, and Dissociation......Page 722
B. Surface Charging......Page 728
C. Distribution of Ions at the Charged Surface......Page 733
A. Problems, Probable Solutions......Page 739
B. Cases from Recent Literature......Page 747
REFERENCES......Page 749
I. INTRODUCTION......Page 752
II. GENERAL FEATURES......Page 753
A. Self-Consistent Field Theory......Page 756
B. Scaling Theory......Page 764
C. Simple Model......Page 768
IV. ADSORPTION KINETICS......Page 774
A. The Stage of Fast Adsorption......Page 776
B. The Stage of Slow Adsorption......Page 781
C. Dynamics of a Macromolecule in the Adsorption Layer......Page 783
D. Adsorption of Homodisperse Polymers......Page 785
E. Replacement Adsorption......Page 789
F. Polymer Adsorption Accompanied by Flocculation......Page 791
G. Adsorption Accompanied by Reaction......Page 798
A. Unchanged Polymers......Page 801
B. Charged Polymers......Page 804
APPENDIX 2......Page 807
REFERENCES......Page 808
I. INTRODUCTION......Page 812
A. Proteins......Page 813
B. Protein Adsorption......Page 816
A. Dimensional Analysis......Page 818
B. A Simple Mechanism for Protein Adsorption......Page 824
C. Limitations on the Applicability of the Model [Eq. (31)]......Page 827
IV. MODEL TESTING......Page 828
A. Parameters a and AC......Page 834
B. Molecular Influences on AC......Page 842
D. Implications Associated with the Model Application to Multi-Domain Proteins......Page 843
E. The Affinity and Extent of Adsorption......Page 845
VII. NOMENCLATURE......Page 847
Greek Symbols......Page 848
APPENDIX 1......Page 849
REFERENCES......Page 851
A. Proteins......Page 856
B. Protein Adsorption Kinetics......Page 857
III. A KINETIC MODEL FOR PROTEIN ADSORPTION......Page 860
A. Low Surface Coverage ðu 0Þ......Page 863
IV. APPLICABILITY OF THE MODEL......Page 864
B. Determination of the Adsorption Rate Constant, ka......Page 867
C. The Extent of Surface-Induced Unfolding......Page 873
V. NOMENCLATURE......Page 877
REFERENCES......Page 878
Index......Page 880
Back Page......Page 888

✦ Subjects

Химия и химическая промышленность;Физическая и коллоидная химия;Поверхностные явления и дисперсные системы;