Catalysis: Principles & Basic Concepts

(1)

CA T AL Y SIS Principles & Basic Concepts

A.V. Salker

A.V . Salker

MEDTECH

A Division of Scientific International

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The book Catalysis: Principles and Basic Concepts covers a wide range of topics and issues such as heterogeneous, homogeneous, photo-catalysis, bio-catalysis, phase transfer catalysis, energy and environment. Enough importance is given to the quality and stress to each chapter.

The materials in this book are presented in a simple and lucid manner so that any science stream person can understand the concepts, role and issues without any difficulty. This book is useful to UG and PG students of chemistry and chemical engineering, researcher and scientists in catalysis, teachers of catalytic stream of chemical sciences including chemists and chemical engineers from industry. One of the most important aspects of energy is to develop method for exploiting, converting, and optimizing energy sources. Catalysis serves as a crosscutting science in this aspect, with the potential to lead and to bring out of the energy crisis. All round efforts are made to include as many as required chapters for the introductory courses and some advance stage level courses on catalysis for chemical sciences. Catalysis is an interdisciplinary subject and required to be flourished to undergraduate and graduate curriculum in chemistry and chemical technology. This book shall help as a suitable text or reference book for such curriculum.

Arun V. Salker, is presently a Professor at Department of Chemistry, Goa University, Goa. He obtained Ph.D. degree from IIT-Bombay and did his Post-Doctoral Research at University of Karlsruhe, Germany. He was a visiting Professor at Kungpook National University, South Korea, in 2003-04. He served Goa University for last 30 years in Research and teaching in Catalysis, Material Chemistry and Environmental Chemistry. He was the Head of Chemistry Department, during the period 2009 to 2012 and 'Dean” Faculty of Natural Science, for the period May 2014 to May 2017. He has nearly ninety research publications in reputed international and national journals, hundred paper presentations in Symp./conferences, granted two Indian patents to his credit and guided several Ph.D. students and published two books including this one. In recognition to his contribution of teaching and research, the Department of Higher Education, Govt. of Goa, conferred on him “Goa State Award for Meritorious Teacher” in Higher Education for the year 2015.

CATALYSIS

Principles & Basic Concepts

CATALYSIS

PRINCIPLES AND BASIC CONCEPTS

ISBN 978-93-88716-51-2

(2)

CATALYSIS

Principles & Basic Concepts

(3)

MEDTECH

Engaging Sciences—Developing Minds!A Division of Scientific International

CATALYSIS

Principles & Basic Concepts

Department of Chemistry

A.V. Salker

Ph.D.

Goa University, Goa India

(4)

MEDTECH A Division of

Scientific International Pvt. Ltd.

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ISBN: 978-93-88716-51-2 (PB) ISBN: 978-93-88716-52-9 (HB)

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CATALYSIS

Principles & Basic Concepts

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_CONTENTS

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3.11

3.t2

3.13 o o a

Heat

of

Adsoqption

Applications of Adsorptions

Scattering, Trapping and Sticking

What is Adsorption?

The Adsorption Isotherm

Freundlich Adsorption Isotherms

The Langmuir Adsorption Isotherm

3.10.1

Testing the Langmuir Equation ^'

The BET Isotherm

3.11.1

Criticism

of

the

BET

theory

3.11.2

Surface Area

from

BET Isotherm

Types of Adsorption Isotherms

BJH Method

Suggested Reading

Exercise

Obj ectiv e Type Questions

26 27 27 28 29

3t

32 34 35 39 40

4t

43 44 44 45

48-71

48 49 49 49 50 52 52 52 53 55 55 56 57 57 51 58 58 59 60 61

6t

62 63 63

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5.1 ^_

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5.1 .5

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5.1.1 l

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5.1. ¹

5.2.1 Lou Partic 5.4.1 5.4.) 5.4.3 Struct 5.5.1 5.5.2 5.5.3 5.2

5.5 5.3 5.4

| _-\.,..,

o il: ^"

o L.t'- :

Charrm.

CnarrrR 4 : [pes ^of Catalysts...

5.1

4.1

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4.2

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of

Catalysts Generally Used

4.3

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of

Metal Catalysts

4.4

Non-metallic Catalysts

4.5

Supported Metal Catalysts

4.5.1

Bimetallic Caralysts

4.5.2

Bi-functionalCatalysts

4.5.3

Magnetic Ferrite Support

4.6

^Zeolites

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4.6.2

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4.6.3 Acidity of

Zeolites

4.6.4

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of

Zeolites

4.7

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4.1

.1

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of

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4.7.2

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4.1

.3

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4.1

.4

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4.1

.5

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4.1

.6

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4.7.7

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4.7.8

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4.7.9

Graphene

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o

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CHaprnn 6 : Surface Reactions and Kinetics... ...106-124

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¹⁰⁹

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of

Ethy

lene

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¹¹⁰

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111

6.2.6

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112

6.2.7

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6.2.8

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113

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.2

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.3

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l2O

6.1

.5

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Suggested

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o

Objectire T\.pe

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cnrprpn 7 : catalvst Deactivations and Regenerations... ...12s-134

1.1 Introduction _D5

7.2 Actirrn

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1.3

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lO.2 Acid

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10.2.1

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10.2.2

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10.2.3

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10.2.4

General

Acid

Catalysis

I0.2.5

General Base Catalysis

t0.2.6

General Acid-Base Catalysis

10.3

Conclusion

o

Suggested Reading

o

Exercise

o

^ObjectiveType Question

...161-t67

161

t62

162 163 163 164 164 165 165 166

t66 t66

Cns.prrn 11 : Decomposition of H2O2 168-174

11.1 Introduction

.168

11.2

General Rate

Expression

168

11.3

Decomposition

of HrO, by CrrOrz-

169

ll.4

Decomposition

of HrO, by MoOf- l7l

o

Suggested

Reading I73

o Exercise

174

o

Objective Type

Questions

¹⁷⁴

Cns.prrn t2.t

12.2 12.3 12.4 12.5 12.6 t2.7 12.8 t2.9 12.10 12.11 12.t2

12 : Selected Examples of Homogeneous Catalytic Reactions ^175-194

Introduction

175

Metal Centered Catalysis

in

Complex

Compounds

175

Mosanto Acetic

Acid Process

177

Carboxylation

Reactions ll8

Hydrogenation

180

Hydroformulation

182

The Wacker

Process

183

The Heck

Reaction

185

Suzuki Coupling

Reaction

187

Dimerization

of

Ethane

to

l-Butene

Isomerization of Alkenes

Asymmetric Catalysis

l2.l2.l

^MonsantoL-DOPA Process

12.12.2

S-Naproxen

12.I2.3

L-Menthol

12.12.4

Jacobsen Epoxidation

12.12.5

Sharlpess Epoxidation

Suggested Reading

Exercise

Obj ectiv e Typ e _Question,s

a a a

xI

CONTENTS

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I I |ntro:-

Cnlprnn 16 : Phase Transfer Catalysis...

16.1

Introduction

16.2

Mechanism

of

PTC

16.3

Selected Exampies

16.4

AdYantages

16.5

Disadvantage

16.6

Applications

o

Suggested Reading

o

Erercise

o

Oblective Type Questions

Cnl.prnn 17 : Catalysts for Energy and Environment

11

.1

Introduction

17.2

Catalytic Gasification

11

.3

Electricity

from

Gas Turbine

11

.1

^Steum^Relorming

11.5

Ele,'trocatalysis

11.6

Fuel Cells

17.6.1

Hydrogen-Oxygen Fuel Cell

11.6"2

Alkaline Fuel Cell

11.6.3

Phosphoric

Acid

Fuel Cell

17.6.4

Methanol Fuei Cell

17.6.5

Molten Carbonate Fuel Cell

17.6.6

Solid Oxide Fuel Cell

11

.7

^Enrironmental Pollution

17.8

Catalysts

for

Environmental Pollution Control

11

.9

^EmrssionControl fbr Automobiles

17.10

Diesel Emission Control

11

.I1

^SelectiveCatalvtic Reduction

t

Strgqested Rectding

o

^Erercise

o

^ObjectiveT\'pe Questiotts

Appendix.

1.

^Useful^Constants

2.

^Answers

to

Objective _Questions

Index

))?,_rra

228

...230-249

243 227 221 223

)7t

224 221 221

230

23t

231 232 232 235 23 236 231 231 238 239

=

xtv CONTENTS