Adsorption by Powders and Porous Solids

Note: Supplemental materials are not guaranteed with Rental or Used book purchases.

ISBN: 9780125989206 | 0125989202
Cover: Hardcover
Copyright: 10/19/1998

eBook

Available Instantly

Online: 1825 Days

Downloadable: Lifetime Access

*To support the delivery of the digital material to you, a digital delivery fee of $3.99 will be charged on each digital item.

$198.00*

The declared objective of this book is to provide an introductory review of the various theoretical and practical aspects of adsorption by powders and porous solids with particular reference to materials of technological importance. The primary aim is to meet the needs of students and non-specialists, who are new to surface science or who wish to use the advanced techniques now available for the determination of surface area, pore size and surface characterization. In addition, a critical account is given of recent work on the adsorptive properties of activated carbons, oxides, clays and zeolites.

Preface

xiii

(2)

List of Main Symbols

Chapter 1. Introduction

(26)

1.1. Importance of adsorption

(1)

1.2. Historical aspects

(4)

1.3. General definitions and terminology

(4)

1.4. Physisorption and chemisorption

(1)

1.5. Adsorption interactions

(2)

1.6. Mobility of adsorbed molecules

(2)

1.7. Energetics of physisorption

(4)

1.8. Types of adsorption isotherms

(3)

1.8.1. Physisorption of gases

(2)

1.8.2. Chemisorption of gases

(1)

1.8.3. Adsorption from solution

(1)

1.9. Molecular modelling of adsorption

(4)

1.9.1. Intermolecular potential functions

(1)

1.9.2. Molecular simulation

(1)

Monte Carlo (MC) simulation

(1)

Molecular dynamics (MD)

(1)

1.9.3. Density functional theory (DFT)

(2)

References

(2)

Chapter 2. Thermodynamics of Adsorption at the Gas-Solid Interface

(25)

2.1. Introduction

(1)

2.2. Quantitative expression of adsorption

(4)

2.3. Thermodynamic potentials of adsorption

(4)

2.4. Thermodynamic quantities related to the adsorbed states in the Gibbs representation

(2)

2.4.1. Definitions of the molar surface excess quantities

(1)

2.4.2. Definitions of the differential surface excess quantities

(1)

2.5. Thermodynamic quantities related to the adsorption process

(5)

2.5.1. Definitions of the differential quantities of adsorption

(1)

2.5.2. Definitions of the integral molar quantities of adsorption

(1)

2.5.3. Advantages and limitations of differential and integral molar quantities of adsorption

(1)

2.5.4. Evaluation of integral molar quantities of adsorption

(1)

Integral molar energy of adsorption

(1)

Integral molar entropy of adsorption

(1)

2.6. Indirect derivation of the quantities of adsorption from a series of experimental physisorption isotherms: the isosteric method

(2)

2.6.1. Differential quantities of adsorption

(1)

2.6.2. Integral molar quantities of adsorption

(1)

2.7. Derivation of the adsorption quantities from calorimetric data

(2)

2.7.1. Discontinuous procedure

(1)

2.7.2. Continuous procedure

(1)

2.8. Methods for the determination of differential enthalpies of adsorption

(2)

2.8.1. Gas adsorption calorimetry

(1)

2.8.2. Immersion calorimetry

(1)

2.8.3. The isosteric method

(1)

2.8.4. The chromatographic method

(1)

References

(3)

Chapter 3. Methodology of Adsorption at the Gas-Solid Interface

(41)

3.1. Introduction

(1)

3.2. Basic aspects of methodology

(14)

3.2.1. Determination of the amount adsorbed

(1)

Gas adsorption manometry

(4)

Gas flow techniques

(3)

Gas adsorption gravimetry

(2)

3.2.2. Gas adsorption calorimetry

(1)

Adiabatic adsorption calorimetry

(1)

Diathermal-conduction adsorption calorimetry

(2)

Diathermal-compensation adsorption calorimetry

(1)

Isoperibol adsorption calorimetry

(1)

3.3. Operational procedures

(8)

3.3.1. Discontinuous procedures for determining the adsorption isotherms

(1)

The discontinuous manometric procedure

(1)

The discontinuous gravimetric procedure

(1)

The discontinuous carrier gas flow procedure

(1)

3.3.2. Continuous procedures for determining the adsorption isotherm

(1)

The continuous gravimetric procedure

(1)

The continuous sonic nozzle procedure

(1)

The continuous manometric procedure

(1)

The continuous differential manometric procedure

(1)

3.3.3. Calorimetric procedures

(1)

Discontinuous manometry

(1)

Continuous sonic nozzle procedure

(2)

Gravimetry

(1)

3.3.4. Simultaneous gravimetry and manometry

(1)

3.4. Details of the operational stages

(15)

3.4.1. Calibration of volumes

(1)

Dosing volumes

(1)

Dead space volumes

(3)

3.4.2. Sample mass

(1)

3.4.3. Outgassing the adsorbent sample

(1)

Aim of the outgassing

(1)

Conventional vacuum outgassing

(1)

Controlled vacuum outgassing by means of CRTA

(2)

Outgassing with a carrier gas

(1)

3.4.4. Buoyancy correction

(1)

Direct approach

(1)

Indirect approach

(1)

Symmetrical balance

(1)

3.4.5. Adsorption equilibrium

(1)

3.4.6. Temperature

(1)

3.4.7. Pressure

(2)

3.4.8. Correction for non-ideality

(1)

3.4.9. Presentation and use of the experimental data

(1)

References

(3)

Chapter 4. Interpretation of Physisorption Isotherms at the Gas-Solid Interface

(24)

4.1. Introduction

(1)

4.2. Physisorption isotherms on non-microporous solids

(9)

4.2.1. Henry's law and virial equations

(2)

4.2.2. The Hill-de Boer equation

(1)

4.2.3. Langmuir theory

(1)

4.2.4. Brunauer-Emmett-Teller (BET) theory

(4)

4.2.5. Multilayer equations

102

(1)

4.3. Phase changes in physisorbed layers

103

(4)

4.4. Physisorption by microporous solids

107

(6)

4.4.1. Introduction

107

(1)

4.4.2. Henry's law and virial analysis

108

(1)

4.4.3. Langmuir-Brunauer theory

109

(1)

4.4.4. Dubinin-Stoeckli theory

110

(2)

4.4.5. Empirical isotherm equations

112

(1)

4.5. Conclusions

113

(1)

References

114

(3)

Chapter 5. Adsorption at the Liquid-Solid Interface: Thermodynamics and Methodology

117

(48)

5.1. Introduction

118

(1)

5.2. Energetics of immersion of solid in pure liquid

119

(21)

5.2.1. Thermodynamic background

119

(1)

Definition of immersion quantities

119

(2)

Relation between the energies of immersion and gas adsorption

121

(1)

Relation between the energies of immersion and adhesion

121

(3)

Relation between the areal surface excess energy and the surface tension

124

(1)

Various types of wetting

125

(1)

Wettability of a solid surface: definition and assessment

126

(3)

5.2.2. Experimental techniques of immersion microcalorimetry in pure liquid

129

(1)

Recommended immersion microcalorimetric equipment and experimental procedure

129

(2)

Evaluation of the correction terms

131

(1)

Critical aspects of immersion microcalorimetric techniques

131

(4)

5.2.3. Applications of immersion microcalorimetry in pure liquid

135

(1)

Evaluation of the wettability

135

(1)

Determination of the polarity of solid surfaces

135

(2)

Study of surface modification

137

(1)

Assessment of the site-energy distribution

138

(1)

Assessment of structural modifications of the adsorbent

139

(1)

Assessment of microporosity

139

(1)

Assessment of surface area

139

(1)

Further comments on the application of immersion microcalorimetry

140

(1)

5.3. Adsorption from liquid solution

140

(20)

5.3.1. Quantitative expression of the amounts adsorbed from a binary solution

142

(1)

Scope and limitation of the normal surface excess amounts

142

(1)

The use of relative surface excess amounts

143

(1)

The use of reduced surface excess amounts

144

(1)

The meaning of relative and reduced surface excess amounts

145

(1)

Adsorption isotherms expressed in reduced surface excess amounts

146

(2)

5.3.2. Quantitative expressions of the energies involved in adsorption from solution

148

(1)

Definitions of energies or enthalpies of adsorption from solution

148

(1)

Definition of displacement enthalpies (and energies)

149

(1)

Definition of the enthalpies (and energies) of mixing

149

(1)

5.3.3. Basic experimental methods for the study of adsorption from solution

150

(1)

Methods for determining the amounts adsorbed

150

(3)

Methods for determining adsorption energies

153

(4)

5.3.4. Applications of adsorption from solution

157

(1)

Assessment of surface area and pore size

157

(1)

Adsorption (and displacement) mechanisms

157

(3)

References

160

(5)

Chapter 6. Assessment of Surface Area

165

(26)

6.1. Introduction

165

(1)

6.2. The BET method

166

(8)

6.2.1. Introduction

166

(1)

6.2.2. The BET plot

166

(3)

The single point method

169

(1)

6.2.3. Validity of the BET monolayer capacity

169

(1)

6.2.4. The BET area

170

(4)

6.3. Empirical methods of isotherm analysis

174

(5)

6.3.1. Standard adsorption isotherms

174

(2)

6.3.2. The t-method

176

(1)

6.3.3. The Alpha(s)-method

176

(3)

6.4. Adsorption from solution

179

(1)

6.5. Immersion microcalorimetry

180

(3)

6.5.1. The modified Harkins and Jura `absolute method'

180

(2)

6.5.2. The surface area of microporous carbons

182

(1)

6.6. The fractal approach

183

(4)

References

187

(4)

Chapter 7. Assessment of Mesoporosity

191

(28)

7.1. Introduction

191

(1)

7.2. Capillary condensation and the Kelvin equation

192

(5)

7.2.1. Derivation of the Kelvin equation

192

(1)

7.2.2. Application of the Kelvin equation

193

(4)

7.3. Mesopore volume, porosity and mean pore size

197

(2)

7.3.1. Mesopore volume

197

(1)

7.3.2. Porosity

198

(1)

7.3.3. Hydraulic radius and mean pore size

199

(1)

7.4. Computation of the mesopore size distribution

199

(5)

7.4.1. General principles

199

(2)

7.4.2. Computation procedure

201

(1)

7.4.3. The multilayer thickness

202

(1)

7.4.4. Validity of the Kelvin equation

203

(1)

7.5. Hysteresis loops

204

(9)

7.6. Density functional formulation

213

(2)

References

215

(4)

Chapter 8. Assessment of Microporosity

219

(18)

8.1. Introduction

219

(3)

8.2. Isotherm analysis

222

(5)

8.2.1. Empirical methods

222

(2)

8.2.2. Dubinin-Stoeckli methods

224

(2)

8.2.3. Nonane pre-adsorption

226

(1)

8.2.4. Generalized adsorption isotherm (GAI)

226

(1)

8.3. Microcalorimetric methods

227

(3)

8.3.1. Immersion microcalorimetry

227

(1)

Immersion of various dry samples in the same liquid

227

(1)

Immersion of dry samples in liquids of different molecular size

228

(1)

Immersion of samples partially pre-covered by vapour adsorption

229

(1)

8.3.2. Gas adsorption microcalorimetry

229

(1)

8.4. Modelling micropore filling: theory and simulation

230

(4)

8.4.1. Potential energy functions

230

(1)

8.4.2. Horvath-Kawazoe (HK) method

231

(2)

8.4.3. Computer simulation and density functional theory

233

(1)

References

234

(3)

Chapter 9. Adsorption by Active Carbons

237

(50)

9.1. Introduction

237

(3)

9.2. Formation and structure of carbon blacks

240

(2)

9.3. Physisorption of gases by carbon black and graphite

242

(10)

9.3.1. Adsorption of nitrogen

242

(5)

9.3.2. Adsorption of noble gases

247

(3)

9.3.3. Adsorption of organic vapours

250

(2)

9.4. Carbonization and activation

252

(3)

9.5. Physisorption of gases by activated carbons

255

(24)

9.5.1. Adsorption of argon, nitrogen and carbon dioxide

255

(9)

9.5.2. Adsorption of organic vapours

264

(9)

9.5.3. Adsorption of helium

273

(3)

9.5.4. Adsorption of water vapour

276

(3)

9.6. Immersion microcalorimetry and adsorption from solution

279

(2)

9.6.1. Immersion microcalorimetry

279

(1)

9.6.2. Adsorption from solution

280

(1)

References

281

(6)

Chapter 10. Adsorption by Metal Oxides

287

(68)

10.1. Introduction

287

(1)

10.2. Physisorption of gases by silica powders and gels

288

(23)

10.2.1. Pyrogenic and crystalline silicas

288

(9)

10.2.2. Precipitated silicas

297

(2)

10.2.3. Silica gels

299

(8)

Dehydroxylated gels

307

(4)

10.3. Aluminas: structure, texture and physisorption

311

(12)

10.3.1. Activated alumina

311

(1)

10.3.2. Aluminium trihydroxides

311

(2)

10.3.3. Aluminium oxide-hydroxides

313

(1)

10.3.4. Alumina structures

314

(1)

10.3.5. Physisorption by high-temperature aluminas

315

(3)

10.3.6. Thermal decomposition of trihydroxides

318

(5)

10.3.7. Decomposition of boehmite and hydrous alumina

323

(1)

10.4. Titanium dioxide powders and gels

323

(10)

10.4.1. Titanium dioxide pigments

323

(2)

10.4.2. Rutile: surface chemistry and gas adsorption

325

(6)

10.4.3. The porosity of titania gels

331

(2)

10.5. Magnesium oxide

333

(7)

10.5.1. Physisorption of non-polar gases on non-porous MgO

333

(3)

10.5.2. Physisorption by porous forms of MgO

336

(4)

10.6. Miscellaneous oxides

340

(11)

10.6.1. Chromium oxide gels

340

(4)

10.6.2. Ferric oxide: thermal decomposition of FeOOH

344

(2)

10.6.3. Microcrystalline zinc oxide

346

(1)

10.6.4. Hydrous zirconia gels

347

(4)

References

351

(4)

Chapter 11. Adsorption by Clays, Pillared layer Structures and Zeolites

355

(46)

11.1. Introduction

355

(3)

11.2. Structure and morphology of layer silicates

358

(3)

11.2.1. Kaolinite

358

(1)

11.2.2. Smectites and vermiculites

359

(1)

11.2.3. Palygorskites

360

(1)

11.2.4. Morphology of clay particles and aggregates

361

(1)

11.3. Physisorption of gases by kaolinite

361

(3)

11.3.1. Nitrogen isotherms

361

(2)

11.3.2. Energetics of argon and nitrogen adsorption

363

(1)

11.4. Physisorption of gases by smectites and vermiculites

364

(9)

11.4.1. Adsorption of non-polar molecules

364

(2)

11.4.2. Sorption of polar molecules

366

(4)

11.4.3. Physisorption by expanded smectites

370

(3)

11.5. Formation and properties of pillared clays

373

(2)

11.5.1. Pillaring

373

(2)

11.5.2. Chemical and physical nature of pillared clays

375

(1)

11.6. Physisorption of gases by pillared clays

375

(3)

11.7. Structure, morphology and synthesis of zeolites

378

(4)

11.7.1. Zeolite structures

378

(1)

Zeolite A

379

(1)

Zeolites X and Y

380

(1)

Pentasil zeolites

380

(1)

Role of exchangeable cations

380

(1)

11.7.2. Zeolite synthesis

381

(1)

11.7.3. Zeolite morphology

382

(1)

11.8. Adsorbent properties of molecular sieve zeolites

382

(14)

11.8.1. Physisorption of gases by zeolite A

382

(3)

11.8.2. Physisorption of gases by zeolites X and Y

385

(4)

11.8.3. Physisorption of gases by ZSM-5 and Silicalite-I

389

(7)

References

396

(5)

Chapter 12. Properties of Some Novel Adsorbents

401

(38)

12.1. Introduction

401

(3)

12.1.1. Precipitation-gelation

402

(1)

12.1.2. Grinding

402

(1)

12.1.3. Heat treatment (calcination)

402

(2)

12.2. Carbons

404

(11)

12.2.1. Superactive carbons

404

(3)

12.2.2. Activated carbon fibres and carbon cloth

407

(6)

12.2.3. Buckyballs and buckytubes

413

(2)

12.3. Nanoporous inorganic materials

415

(19)

12.3.1. MCM-41 and related structures

415

(1)

Formation

415

(2)

Physisorption studies

417

(8)

12.3.2. Aluminophosphate molecular sieves

425

(1)

Background

425

(1)

Physisorption of gases by AlPO(4)-5

426

(5)

Physisorption of gases by VPI-5

431

(3)

References

434

(5)

Chapter 13. General Conclusions and Recommendations

439

(9)

13.1 Physisorption at the gas-solid interface

439

(7)

13.1.1. Interpretation and classification of adsorption isotherms

439

(1)

Type I isotherms

440

(1)

Type II isotherms

440

(1)

Type III isotherms

441

(1)

Type IV isotherms

441

(1)

Type V isotherms

442

(1)

Type VI isotherms

442

(1)

Intermediate and composite isotherms

442

(1)

13.1.2. Energetics of physisorption

442

(1)

13.1.3. Determination of surface area

443

(1)

13.1.4. Capillary condensation and mesopore analysis

444

(1)

13.1.5. Micropore analysis

445

(1)

13.2. Adsorption at the liquid-solid interface

446

(2)

13.2.1. Immersion energetics

446

(1)

13.2.2. Adsorption from solution

446

(2)

Author Index

448

(12)

Subject Index

460

Please wait while the item is added to your bag...

FREE SHIPPING

Rent More, Save More! Use code: BBRENTAL

5% off 1 book, 7% off 2 books, 10% off 3+ books

Adsorption by Powders and Porous Solids

Summary

Table of Contents

Supplemental Materials

FREE SHIPPING

Rent More, Save More! Use code: BBRENTAL

5% off 1 book, 7% off 2 books, 10% off 3+ books

Adsorption by Powders and Porous Solids

Summary

Table of Contents

Supplemental Materials

Digital License